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Fundamentals of Electronic Spectroscopy

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Fundamentals of Electronic Spectroscopy

Hans Jakob Wörner1,2 and Frédéric Merkt1

1
Laboratorium für Physikalische Chemie, ETH Zürich, Zürich, Switzerland
2
Joint Laboratory for Attosecond Science, National Research Council of Canada and University of Ottawa, Ottawa, Ontario,
Canada

1 INTRODUCTION including spin, Q stands for the 3N − 6(5) normal coordi-

nates used to describe the vibrations of the nuclear frame-
Electronic spectroscopy aims at studying the structure and work, (θ , φ, χ) are the Euler angles specifying the relative
dynamics of atoms and molecules by observing transitions orientation of the space-fixed and molecule-fixed axis sys-
between different electronic states induced by electromag- tems, and mα describes the spin state of the nuclei. The
netic radiation. spectrum of an electronic transition α
← α

between a
The notion of an electronic state of a molecule follows lower electronic state α

and an upper electronic state α

from the Born–Oppenheimer approximation, which enables of a molecule never consists of a single line, but usually
one to separate the Schrödinger equation into an equation of a very large number of lines corresponding to all pos-
describing the motion of the electrons at fixed configura- sible vibrational (vi
), rotational (J
, Ka
, Kc
), and hyper-
tions of the much heavier nuclei, and an equation describing fine levels of the upper electronic state accessible from all
the motion of the nuclei on the 3N − 6- (3N − 5-) dimen- populated vibrational (vi

), rotational (J

, Ka

, Kc

), and
sional adiabatic electronic potential energy surface of a hyperfine levels of the lower electronic state. An electronic
nonlinear (linear) molecule consisting of N atoms. This spectrum, thus, consists of a system of vibrational bands,
separation and the very different timescales of the differ- each of which possesses a rotational fine structure. Neglect-
ent types of motion in a molecule lead to the approximate ing the hyperfine structure, the transition wave numbers can
description of stationary states as products of electronic be expressed as differences of rovibronic term values:
ϕ e (qi ), vibrational ϕ (e) (ev)
v (Qα ), rotational ϕ r (θ , φ, χ), and
nuclear-spin φ (evr)
ns (mα ) wave functions
ν̃ = Te
+ G
(v1
, v2
, . . .) + F
(J
, Ka
, Kc
) − Te


− G

(v1

, v2

, . . .) − F

(J

, Ka

, Kc

) (3)
Ψ = ϕ e (qi )ϕ (e) (ev) (evr)
v (Q)ϕ r (θ , φ, χ)φ ns (mα ) (1)
where Te

and Te
represent the electronic term values (i.e.,
and sums of electronic Ee , vibrational Ev , rotational Er ,
the positions of the minima of the Born–Oppenheimer
and hyperfine Ens energies
potential surfaces of the corresponding electronic states),
E = Ee + Ev + Er + Ens (2) G

and G
represent the vibrational term values discussed
in detail in Albert et al. 2011: Fundamentals of Rota-
(see Merkt and Quack 2011:Molecular Quantum Mechan- tion–Vibration Spectra, this handbook, and F

and F

ics and Molecular Spectra, Molecular Symmetry, and represent the rotational term values discussed in detail in
Interaction of Matter with Radiation, this handbook) In Bauder 2011: Fundamentals of Rotational Spectroscopy,
equation (1), qi represents the coordinates of the electrons this handbook. An electronic spectrum offers the possi-
bility of obtaining information not only on the electronic
Handbook of High-resolution Spectroscopy. Edited by Martin Quack structure of a molecule but also on the vibrational, rota-
and Frédéric Merkt.  2011 John Wiley & Sons, Ltd. tional, and hyperfine structures of the relevant electronic
ISBN: 978-0-470-74959-3. states. The purely electronic origin of the transition is at
176 Fundamentals of Electronic Spectroscopy

ν̃ e = Te
− Te

, and each band of the system has its origin one of the irreducible representations of the point group.
at ν̃ e + G
− G

, so that the origin of the band system is at The eigenfunctions Ψ n of Ĥ , thus, transform as one of the
ν̃ 00 = ν̃ e + G
(0, 0, . . . , 0) − G

(0, 0, . . . , 0). irreducible representations of the corresponding symmetry
The hierarchy of motion upon which equations (1) group, and the irreducible representations are used to label
and (2) rely implies that the energetic separation between the electronic states.
electronic states is much larger than that between vibra- The ground electronic state is labeled by the letter X for
tional and rotational levels of a given electronic state. diatomic molecules and X̃ for polyatomic molecules. Elec-
Consequently, the populations in the electronically excited tronically excited states are designated in order of increas-
states are negligible at room temperature, and electronic ing energy by the letters A, B, C, . . . (Ã, B̃, C̃, . . . for
transitions, particularly those from the ground electronic polyatomic molecules) if they have the same total electron-
state, are usually observed at shorter wavelengths than spin quantum number S as the ground electronic state, or by
vibrational and pure rotational transitions, i.e., in the visible the letters a, b, c, . . . (ã, b̃, c̃, . . . for polyatomic molecules)
or the ultraviolet regions of the electromagnetic spectrum. if they have a different spin multiplicity. The “ ˜ ” in the
The rovibrational levels of electronically excited states are designation of electronic states of polyatomic molecules is
usually located at energies where the density of rovibronic introduced to avoid confusion with the letters A and B that
states is very large, or even above one or more dissociation are used as group-theoretical labels. This labeling scheme
and ionization limits, in which case they form resonances occasionally poses problems, for instance, when an elec-
in the dissociation and/or ionization continua. tronic state thought to be the first excited state when it
Interactions with neighboring electronic states and radia- was first observed turns out later to be the second or the
tionless decay processes such as autoionization, predissoci- third, or when several local minima of the same potential
ation, internal conversion (IC), and intersystem crossings energy surface exist and lead to distinct band systems in an
(ISC) are unavoidable and represent a breakdown of electronic spectrum, or because of initial misassignments.
equations (1) and (2). These interactions can cause pertur- Whereas misassignments of symmetry labels are usually
bations of the spectral structures and can limit the lifetimes corrected, incorrect A, B, . . . labels sometimes survive,
of the upper levels of the transitions, leading to a broaden- especially when they have been accepted as names.
ing of the spectral lines and to diffuse spectra. The complex As the molecules become larger and/or less symmetric,
structure of electronic spectra and the frequent breakdown this nomenclature tends to be replaced by a simpler one that
of the Born–Oppenheimer approximation in electronically uses a letter (S for singlet (S = 0), D for doublet (S = 1/2),
excited states render electronic spectra more difficult to T for triplet (S = 1), . . .) to indicate the electron-spin
interpret than vibrational and pure rotational spectra. Their multiplicity, and a subscript i = 0, 1, 2, . . . to indicate
information content, however, may be larger, particularly the energetic ordering, 0 being reserved for the ground
when the spectral structures are sharp. electronic state. For example, the lowest three electronic
Despite the frequent breakdown of the Born–Oppenhe- states of benzene are sometimes designated as X̃ 1 A1g ,
imer approximation, the way electronically excited states
ã 3 B1u , and à 1 B2u using D6h -point-group symmetry labels,
and electronic transitions are labeled relies on the approxi-
or as S0 , T1 , and S1 using the second, simpler labeling
mate description provided by equations (1) and (2), partic-
scheme. The different electronic states of a molecule
ularly for small molecules: vibrational and rotational levels
can have Born–Oppenheimer potential energy surfaces of
are labeled as explained in Albert et al. 2011: Funda-
very different shapes and which reflect different binding
mentals of Rotation–Vibration Spectra and Bauder 2011:
mechanisms. Figure 1, which displays only a small subset
Fundamentals of Rotational Spectroscopy, respectively,
of the adiabatic potential energy functions of molecular
in this handbook; the electronic states are labeled with a
hydrogen, illustrates this diversity and the complexity of
letter, representing the “name” of the state, followed by a
the electronic structure of this seemingly simple molecule.
symmetry label or a term symbol that can be derived either
In selected regions of internuclear distances, the states can
from the spectra themselves or from the symmetry of the
be classified as:
occupied molecular orbitals, if these are known.
The eigenstates of a molecule with an associated Hamil-
tonian Ĥ remain invariant under the symmetry operations • Valence states, i.e., states in which the valence electrons
Si of the point group. The operators Ŝi corresponding to occupy molecular orbitals with significant amplitudes
the symmetry operations Si , therefore, commute with Ĥ at the positions of more than one atom. Valence states
([Ĥ , Ŝi ] = 0). Consequently, the eigenfunctions Ψ n of Ĥ can be entirely repulsive if the valence electrons occupy
can be chosen such that they are also eigenfunctions of Ŝi predominantly antibonding molecular orbitals or attrac-
and can be designated with the eigenvalues of the opera- tive if they occupy predominantly bonding orbitals, in
tors Ŝi . These eigenvalues correspond to the characters of which case rigid molecular structures usually result.
 Fundamentals of Electronic Spectroscopy 177

34 34
3dsg
4psu
32 3dpg H+ + H+ 32
4fsu 3ssg
2ssg 3psu H + H(3L)
+
30 2ppu 30

H+ + H(2L)
28 28

26 26

24 24
2psu

22 D' 1Πu 4pp 22

Potential energy (electron volts)

V 1Πu 4fp

20 B'' 1Σu+ 4ps 20

D'' 1Πu 5pp
+ g 3Σg+ 3ds
H2 H+ + H(1s)
B' 1Σu+ 3ps
18 H(1s) + H(5L) 18
X 2Σg+ 1ssg 10
H(1s) + H(4L) H+ + H− (1s2)
e 3Σu+ 3ps 5 H(1s) + H(3L)
16
10
m 3Σu+ 4fs 16
h 3Σg+ 3ss i 3Πg 3dp
0 5
5
0 H(1s) + H(2L)
0 0 10
5 25
14 0
0 0 20 14
H(2s) + H−(1s2)
5
0 5 15

0 0 0
10
D Πu 3pp (also d Πu 3pp and J, j
1 3 1,3
∆g 3dd
12 0 0 5 I 1Πg 3dp 12
C 1Πu 2pp
0
B 1Σu+ 2ps
C + e− 2Σg+ a 3Σg+ 2ss
10 c+ e− 2Σg+ H 1Σg+ 3ss 10
c 3Πu 2pp
E,F 1Σg+ 2ss + 2ps2
8 8
H2
b 3Σu+ 2ps
6 6
b + e− 2Σg+ H(1s) + H(1s)
4 10
H(1s) + H−(1s2) 4
−
5 H2
2 X + e− 2Σu+ 2
X 1Σg+ 1ss
0
0 0
0 0.4 1.2 1.6 2.0 2.4 2.8 3.2 3.6 4.0 4.4 4.8 5.2 5.6
0.8
Internuclear distance (Å)

Figure 1 Potential energy functions of selected electronic states of H2 , H2 + , and H2 − . [Adapted from Sharp (1971).]

• Rydberg states, i.e., states in which one of the valence infinite series of states with almost identical potential
electrons has been excited to a diffuse orbital around energy functions (or hypersurfaces), and can also be
a positively charged molecular ion core, resembling an labeled by the orbital angular momentum quantum
excited orbital of the hydrogen atom. In such a state, the number  of the Rydberg electron. Rydberg states of
excited electron, called the Rydberg electron, is bound H2 can easily be identified in Figure 1 as the states
to the molecular ion core by the attractive Coulomb with potential energy functions parallel to that of the
potential and can be labeled by a principal quantum X 2 + g ground state of H2 .
+

number n. At sufficiently high values of n, the Rydberg • Ion-pair states, i.e., states in which the molecule can
electron is located, on average, at large distances be described as composed of two atoms A+ and
from the ion core and only interacts weakly with B− (or two groups of atoms) of opposite charge
it. The Born–Oppenheimer potential energy functions that are held together by a Coulomb potential. The
(or hypersurface in the case of polyatomic molecules) attractive part of the potential energy of these states
of Rydberg states, thus, closely resemble that of the is proportional to −1/R (R is the distance between
electronic state of the molecular ion core to which the atoms of opposite charge) and dissociate at large
the Rydberg electron is attached. Rydberg states form distances into a cation (A+ ) and an anion (B− ). At short
178 Fundamentals of Electronic Spectroscopy

internuclear distances, the potential energy function Theory, Mastalerz and Reiher 2011: Relativistic Elec-
falls rapidly and starts overlapping with valence states tronic Structure Theory for Molecular Spectroscopy,
with which they interact strongly, giving rise to charge Marquardt and Quack 2011: Global Analytical Potential
transfer processes and electronic states with multiple Energy Surfaces for High-resolution Molecular Spec-
potential wells. Ion-pair states are not only encountered troscopy and Reaction Dynamics, Carrington 2011: Using
in molecules such as NaCl but also in homonuclear Iterative Methods to Compute Vibrational Spectra and
diatomic molecules, an example being the potential Tennyson 2011: High Accuracy Rotation–Vibration Cal-
function shown in Figure 1 which coincides with the culations on Small Molecules, this handbook. The calcu-
outer wall of the potential functions of the E,F 1 + g lation of the spectral and dynamical properties of Rydberg
and B 1 +u states. states by ab initio quantum theory is reviewed in Jun-
• States in which the atoms (or group of atoms) are held gen 2011b: Ab Initio Calculations for Rydberg States
together by weak van der Waals interactions, which and by multichannel quantum defect theory in Jungen
give rise to shallow potential wells at large internuclear 2011a: Elements of Quantum Defect Theory, both in
distances. The ground electronic states of the rare-gas this handbook. Experimental and theoretical investigations
dimers are prototypes of such states. of the photodissociation of electronically excited states
are presented in Ashfold et al. 2011: High-resolution
As all classifications, the classification of electronic states Photofragment Translational Spectroscopy using Ryd-
and binding mechanisms as valence, ion-pair, Rydberg, and berg Tagging Methods and Schinke 2011: Photodissocia-
van der Waals represents a simplification based on idealized tion Dynamics of Polyatomic Molecules: Diffuse Struc-
limiting situations. Because of configuration interactions, tures and Nonadiabatic Coupling, respectively, in this
an electronic state that can be described as a valence state handbook. The valence and inner-shell photoionization
at short internuclear distances, may evolve into a Rydberg dynamics of molecules, including studies of autoionization
state or an ion-pair state at larger distances, or even display processes in electronically excited states, are reviewed in
shallow van der Waals potential wells. Pratt 2011b: High-resolution Valence-shell Photoioniza-
The complexity of the electronic structure of even tion and Miron and Morin 2011: High-resolution Inner-
the simplest molecular systems illustrated in Figure 1 is shell Photoionization, Photoelectron and Coincidence
reflected by the complexity of electronic spectra. Not only Spectroscopy, respectively, in this handbook. The use
does each molecule represent a special case with its par- of electronic spectroscopy to study specific classes of
ticular symmetry properties, number and arrangement of molecular systems and electronic states is illustrated in
atoms, and magnetic and electric properties, but also the Guennoun and Maier 2011: Electronic Spectroscopy of
large number and the diversity of electronic states of any Transient Molecules, Schmitt and Meerts 2011: Rota-
given molecule, the interactions between these states, and tionally Resolved Electronic Spectroscopy and Auto-
the possibility of interactions with dissociation and ioniza- matic Assignment Techniques using Evolutionary Algo-
tion continua contribute to make an exhaustive treatment rithms, Pratt 2011a: Electronic Spectroscopy in the
of electronic spectroscopy impossible. In this article, we Gas Phase, Callegari and Ernst 2011: Helium Droplets
seek to present, at an introductory level, the general prin- as Nanocryostats for Molecular Spectroscopy—from
ciples that form the basis of electronic spectroscopy and the Vacuum Ultraviolet to the Microwave Regime
emphasize common aspects of the electronic structure and and Eikema and Ubachs 2011: Precision Laser Spec-
spectra of atoms and molecules, particularly concerning the troscopy in the Extreme Ultraviolet, this handbook. The
use of group theory and the classification of interactions. Jahn–Teller (JT) effect and nonadiabatic effects in man-
These aspects are best introduced using atoms, diatomic ifolds of near-degenerate electronic states are treated in
molecules, and small polyatomic molecules. Köppel et al. 2011: Theory of the Jahn–Teller Effect,
More advanced material is presented in other arti- this handbook, the treatment of fine structure in elec-
cles of this handbook: The determination of potential tronically excited states using effective Hamiltonians is
energy surfaces and rovibronic energy levels of poly- the subject of Field et al. 2011: Effective Hamiltonians
atomic molecules by ab initio quantum chemical meth- for Electronic Fine Structure and Polyatomic Vibra-
ods is the object of Yamaguchi and Schaefer 2011: Ana- tions, this handbook, and studies of ultrafast electronic
lytic Derivative Methods in Molecular Electronic Struc- processes taking place on the (sub)femtosecond timescale
ture Theory: A New Dimension to Quantum Chem- are reviewed in Wörner and Corkum 2011: Attosecond
istry and its Applications to Spectroscopy, Tew et al. Spectroscopy, this handbook. The use of photoelectron
2011: Ab Initio Theory for Accurate Spectroscopic Con- spectroscopy to study the electronic states of molecular
stants and Molecular Properties, Breidung and Thiel cations is described by Merkt et al. 2011: High-resolution
2011: Prediction of Vibrational Spectra from Ab Initio Photoelectron Spectroscopy, this handbook. These articles
 Fundamentals of Electronic Spectroscopy 179

also provide information on the wide range of experimental spectra by a treatment of the electronic structure and spectra
techniques and spectroscopic instruments that are employed of atoms. This choice enables the subsequent presentation
to measure electronic spectra. of the electronic structure and spectra of molecules in a
Until the second half of the twentieth century, elec- more compact manner.
tronic spectra were almost exclusively obtained by mon-
itoring the radiation transmitted by a given probe gas, or
the radiation emitted by a sample after the production of 2 ELECTRONIC STRUCTURE
electronically excited atoms or molecules using electric or
microwave discharges, flash lamps, or in flames, as a func- The electronic structure of atoms and molecules is charac-
tion of the wavelength. In the second half of the twentieth terized by the electronic wave function that corresponds to
century, the use of intense and/or highly monochromatic the solution of the electronic Schrödinger equation. When
laser sources has greatly extended the range of applications the effects of electron correlation are not dominant, the
of electronic spectroscopy, enabling studies at very high electronic wave function can be approximated by a single
spectral resolution and unprecedented sensitivity. Multipho- electronic configuration, i.e., a product of single-electron
ton processes started to be exploited systematically to (i) wave functions or orbitals, reflecting the occupancy of these
study electronically excited states not accessible from the orbitals.
ground state by single-photon excitation, (ii) reduce spec- A given electronic configuration gives rise to several
tral congestion in electronic spectra by carrying out the states, or terms, corresponding to the different relative
multiphoton excitation via selected rovibrational levels of orientations of the electronic orbital and spin angular
suitable intermediate electronic states, and (iii) efficiently momentum vectors. To distinguish the different terms of
detect the resonant multiphoton transitions by monitoring a given configuration, term symbols are used that indicate
the resonance-enhanced multiphoton ionization (REMPI) the electronic symmetry and the relative orientation of the
signal. orbital and spin angular momentum vectors. The symmetry
In combination with laser radiation, highly sensitive properties of the orbitals and of the electronic wave
spectroscopic techniques, many of them enabling the functions are conveniently described in the point group of
background-free detection of the electronic transitions, such the molecule of interest.
as laser-induced fluorescence (LIF) spectroscopy, REMPI When electron correlation is important, the electronic
spectroscopy, photofragment excitation spectroscopy, dege- wave function must be described by the sum of contribu-
nerate four-wave mixing spectroscopy, cavity-ring-down tions corresponding to electronic configurations differing in
spectroscopy, and a wide range of modulation techniques the occupation of one, two, or more orbitals. The configura-
have revolutionized the field of high-resolution electronic tions contributing to a given electronic state have the same
spectroscopy, revealing for the first time the finest details electronic symmetry, which is therefore an essential ele-
of the energy level structure of atoms and molecules, and ment of the electronic structure. The symmetry properties
allowing systematic studies of the electronic spectra and of the electronic states also determine whether a transition
structure of unstable and/or highly reactive species such between two electronic states can be induced by electro-
magnetic radiation.
as weakly bound molecular complexes, free radicals, and
The general principles that enable one to classify the
molecular ions.
electronic structure in terms of symmetry properties and
The different techniques currently in use in high-
to exploit these properties in the analysis of electronic
resolution electronic spectroscopy are presented in the
spectra are the same for atoms and molecules. However,
articles of this handbook mentioned above and are not
whereas nonlinear polyatomic molecules belong to point
described in this introductory article. Instead, we provide
groups with a finite number of symmetry elements and,
the elementary knowledge and introduce the most important
thus, a finite number of irreducible representations, atoms
concepts that are necessary to optimally use the scien-
and linear molecules belong to point groups with an infinite
tific literature related to electronic spectra of atoms and
number of symmetry elements and irreducible representa-
molecules. The article consists of two main parts: one
tions. This difference justifies the treatment of the electronic
devoted to the electronic structure of atoms and molecules
structure of atoms, linear, and nonlinear molecules in sep-
and the other to their electronic spectra. Because the
arate sections.
spectra of atoms are not complicated by the vibrational and
rotational fine structures, they reveal most aspects of the
electronic structure and dynamics more purely and clearly 2.1 Atoms
than molecular spectra and are ideally suited to introduce
many important concepts. We have, therefore, chosen to Atoms belong to the point group Kh , the character and
begin the sections on electronic structure and electronic direct-product tables of which are presented in Tables 1
180 Fundamentals of Electronic Spectroscopy

Table 1 Character table of the point group Kh appropriate to label the electronic states of atoms.
ϕ
Kh E ∞Cϕ∞ ∞S∞ i

Sg 1 1 1 1 x 2 + y 2 + z2
Pg 3 1 + 2 cos ϕ 1 − 2 cos ϕ 3 Rx , Ry , Rz
Dg 5 1 + 2 cos ϕ + 2 cos 2ϕ 1 − 2 cos ϕ + 2 cos 2ϕ 5 x 2 + y 2 − 2z2 ,
x2 − y2,
xy, xz, yz
Fg 7 1 + 2 cos ϕ + 2 cos 2ϕ + 2 cos 3ϕ 1 − 2 cos ϕ + 2 cos 2ϕ − 2 cos 3ϕ 7
... ... ... ... ...
Su 1 1 −1 −1
Pu 3 1 + 2 cos ϕ −1 + 2 cos ϕ −3 x, y, z
Du 5 1 + 2 cos ϕ + 2 cos 2ϕ −1 + 2 cos ϕ − 2 cos 2ϕ −5
Fu 7 1 + 2 cos ϕ + 2 cos 2ϕ + 2 cos 3ϕ −1 + 2 cos ϕ − 2 cos 2ϕ + 2 cos 3ϕ −7
... ... ... ... ...

Table 2 Direct-product table of the point group Kh . term representing the interaction with the nucleus. Ĥ

represents the repulsion between the electrons, and Ĥ

all
⊗ S P D F ...
the very small contributions to Ĥ that can be neglected in
S S P D F . . . first approximation (e.g., hyperfine interactions, see below).
P P S, P, D P, D, F D, F, G . . .
D D P, D, F S, P, D, F, G P, D, F, G, H . . .
F F D, F, G P, D, F, G, H S, P, D, F, G, H, I . . . 2.1.1 The Hydrogen Atom and One-electron Atoms
... ... ... ... ... . . .
In one-electron atoms such as H, He+ , Li2+ , . . ., Ĥ
= 0 in
In addition, the rules g ⊗ g = u ⊗ u = g and g ⊗ u = u ⊗ g = u are
obeyed.
equation (4). If Ĥ

is neglected, the Schrödinger equation
can be solved analytically, as demonstrated in most quan-
and 2. The symmetry operations of the point group Kh tum mechanics textbooks. The eigenvalues Enm and
consist of the identity (E), the inversion (i), all rota- eigenfunctions Ψ nm are then described by equations (5)
ϕ
tion (∞Cϕ∞ ), and rotation–reflection (∞S∞ ) symmetry and (6), respectively:
operations of a sphere and of the operations that can be
obtained by combining them. The quantum states of an Enm = −hcZ 2 RM /n2 (5)
atom can, therefore, be designated by the symmetry labels Ψ nm (r, θ , φ) = Rn (r)Ym (θ , φ) (6)
S, P, D, F, . . ., which reflect the symmetry of the wave
functions with respect to rotation and rotation–reflection In equation (5), Z is the nuclear charge and RM is the
operations, and a label g/u (from the German words “ger- mass-corrected Rydberg constant for a nucleus of mass M:
ade”(=even)/“ungerade”(=odd)), which gives the symmetry
with respect to inversion through the symmetry center (i). µ
RM = R∞ (7)
This widely used group-theoretical nomenclature actually me
originates from observations of the spectral characteristics
of the electronic spectra of the alkali-metal atoms: s, sharp where R∞ = me e4 /(8h3
20 c) = 109 737.31568527(73) cm−1
series; p, principal series; d, diffuse series; and f, funda- (Mohr et al. 2008) represents the Rydberg constant for a
mental series. The states of u symmetry are often labeled hypothetical infinitely heavy nucleus and µ = me M/(me +
with a superscript “o” for “odd”. M) is the reduced mass of the electron–nucleus system.
Neglecting the motion of the heavy nucleus, the Hamil- The principal quantum number n can take integer values
tonian operator of a N -electron atom can be written as from 1 to ∞, the orbital angular momentum quantum
  number  integer values from 0 to n − 1, and the mag-

N
p̂i2 Ze2
N
N
e2 netic quantum number m integer values from − to .
Ĥ = − + +Ĥ

(4) In equation (6), r, θ , and φ are the polar coordinates.
2me 4π
0 ri 4π
0 rij
i=1
   i=1 j >i  Rn (r) and Ym (θ , φ) are radial wave functions and spher-
ĥi Ĥ
ical harmonics, respectively. Table 3 lists the possible sets
 of quantum numbers for the first values of n, the corre-
where i ĥi represents a sum of one-electron operators, sponding expressions for Rn (r) and Ym (θ , φ), and the
each containing a kinetic energy term and a potential energy symmetry designation nm of the orbitals.
 Fundamentals of Electronic Spectroscopy 181

Table 3 Quantum numbers, wave functions, and symmetry designation of the lowest eigenstates of the hydrogen atom.

n  m Rn (r) Ym (θ, φ) Orbital designation

Z
3/2 
1 0 0 2 e−ρ/2 1
1s
a

3/2 −ρ/2  4π
2 0 0 2−3/2 Za e (2 − ρ) 1
2s

 4π
3/2
2 1 0 1
√ Z
ρe−ρ/2 3
cos θ 2p0 (or 2pz )
2 6 a


4π
3/2
2 1 ±1 1
√ Z
ρe−ρ/2 − 3 ±iφ
sin θ e 2p±1 (or 2px,y )
2 6 a

 8π
3/2 −ρ/2
3 0 0 3−5/2 Za e (6 − 6ρ + ρ 2 ) 1
3s

 4π
Z 3/2
3 1 0 1
√ ρe−ρ/2 (4 − ρ) 3
cos θ 3p0 (or 3pz )
9 6 a


4π
Z 3/2
3 1 ±1 1
√ ρe−ρ/2 (4 − ρ) − 3
sin θ e±iφ 3p±1 (or 3px,y )
9 6 a
Z
3/2 2 −ρ/2  8π

16π (3 cos θ − 1)
3 2 0 √1 ρ e 5 2 3d0 (or 3dz2 )
9 30 a


3/2
3 2 ±1 √1 Z
ρ 2 e−ρ/2 − 8π 15
sin θ cos θ e±iφ 3d±1 (or 3dxz,yz )
9 30 a


3/2
3 2 ±2 √1
9 30 a
Z
ρ 2 e−ρ/2 15 2
32π sin θ e
±i2φ
3d±2 (or 3dxy,x 2 −y 2 )

Linear combinations of the complex-valued Rn (r)Ym (θ , φ) can be formed that are real and correspond to the orbitals used by chemists with designations
given in parentheses in the last column. a = a0 mµe and ρ = 2Zna r.

The energy eigenvalues given by equation (6) do not core consisting of the nuclei and the other electrons.
depend on the quantum numbers  and m and have These states are called Rydberg states. They have
therefore a degeneracy factor of n2 . They form an infinite already been mentioned in the introduction and are dis-
series which converges at n = ∞ to a value of 0. Positive cussed further in Section 2.1.6.
energies, thus, correspond to situations where the electron • The probability of finding the electron in the immediate
is no longer bound to the nucleus, i.e., to an ionization vicinity of the nucleus, i.e., within a sphere of radius on
continuum. Expressing the energy relative to the lowest the order of a0 , decreases with n−3 . This implies that all
(n = 1) level, physical properties that depend on this probability, such
 as the excitation probability from the ground state, the
1
Enm = hcZ RM 1 − 2 = hcTn
2
(8) radiative decay rate to the ground state, or relativistic
n effects such as the spin–orbit coupling or hyperfine
interactions involving the excited electron, should also
one recognizes that the ionization energy of the 1s level is
scale with n−3 .
hcZ 2 RM , or expressed as a term value in the wave-number
• The same probability decreases exponentially and
unit of cm−1 , Tn=∞ = RM .
rapidly becomes negligible with increasing value of
The functions Ψ nm (r, θ , φ) represent orbitals and
 because the centrifugal barrier in the electron–ion
describe the bound states of one-electron atoms; their norm
interaction potential increases with 2 , effectively sup-
Ψ ∗nm Ψ nm represents the probability density of finding
pressing the tunneling probability of the excited elec-
the electron at the position (r, θ , φ) and imply the following
tron into the region close to the nucleus or close to the
general behavior, which is also important to understand the
atomic/molecular core in the case of Rydberg states
properties of polyelectronic atoms and of molecular Ryd-
of polyelectronic atoms and molecules. Low- states
berg states:
are thus called penetrating Rydberg states and high-
• The average distance between the electron and the  states nonpenetrating. In polyelectronic atoms and
nucleus is proportional to n2 , in accordance with Bohr’s molecules, the latter behave almost exactly as in the
model (Bohr 1914) of the hydrogen atom, which pre- hydrogen atom.
dicts that the classical radius of the electron orbit
should grow with n as a0 n2 , a0 = 0.52917720859(36) The orbital angular momentum quantum number , which
Å being Bohr’s radius. This implies that, in polyelec- comes naturally in the solution of the Schrödinger equation
tronic atoms and in molecules, very similar electron- of the hydrogen atom, is also a symmetry label of the
ically excited states also exist as soon as n is large corresponding quantum states. Indeed, the 2 + 1 functions
enough for the excited electron to be located mainly Ψ nm (r, θ , φ) with m = −, − + 1, . . . ,  transform as
outside the positively charged atomic or molecular ion the 2 + 1 components of the irreducible representations
182 Fundamentals of Electronic Spectroscopy

of the Kh point group listed in Table 1. These irreducible The electron wave function (equation 12) gives the
representations are designated by letters as s ( = 0), p occupation of the atomic orbitals and represents a given
( = 1), d ( = 2), f ( = 3), g ( = 4), with subsequent electron configuration (e.g., Li: Ψ 1 (q1 , q2 , q3 ) = 1sα(q1 ),
labels in alphabetical order, i.e., h, i, k, l, etc., for  = 5, 1sβ(q2 ), 2sα(q3 )). Neglecting the electron-repulsion term
6, 7, 8, etc. The reason for using small letters to label in equation (4) is a very crude approximation, and Ĥ

orbitals, instead of using the capital letters designating the needs to be considered to get a realistic estimation of the
irreducible representations of the Kh point group, is that eigenfunctions and eigenvalues of Ĥ . A way to consider
capital letters are reserved to label electronic states. The Ĥ
without affecting the product form of equation (12) is to
distinction between electronic orbitals and electronic states introduce, for each electron, a potential energy term describ-
is useful in polyelectronic atoms. ing the interaction with the mean field of all other elec-
The nodal structure of the s, p, d, f, . . . spherical trons. Iteratively solving one-electron problems and mod-
harmonics also implies that s, d, g, . . . orbitals with even ifying the mean-field potential term leads to the so-called
values of  have g symmetry, and that p, f, h, . . . orbitals Hartree–Fock self-consistent field (HF-SCF) wave func-
with odd values of  have u symmetry. Orbitals with tions, which still have the form (equation 12) of a single
 = 2k + 1 (k being an integer number) of g symmetry electronic configuration but now incorporate most effects of
and orbitals with  = 2k of u symmetry do not occur. the electron–electron repulsion except their instantaneous
2
The operators
ˆ and ˆz describing the squared norm correlation. Because polyelectronic atoms also belong to
of the orbital angular momentum vector and its projection the Kh point group, the angular part of the improved
along the z axis commute with Ĥ and with each other. The orbitals can also be described by spherical harmonics
spherical harmonics Ym (θ , φ) are thus also eigenfunctions Ym (θ i , φ i ). However, the radial functions Rn (r) and
2
of
ˆ and ˆz with eigenvalues given by the eigenvalue the orbital energies (
i in equation 14) differ from the
equations: hydrogenic case because of the electron–electron repulsion
term Ĥ
.
2 An empirical sequence of orbital energies can be deter-

ˆ Ym (θ , φ) =
2 ( + 1)Ym (θ , φ) (9)
mined that can be used to predict the ground-state config-
and uration of most atoms in the periodic system using Pauli’s
Aufbau principle:
ˆz Ym (θ , φ) =
m Ym (θ , φ) (10)

1s ≤
2s ≤
2p ≤
3s ≤
3p ≤
4s ≤

3d ≤
4p ≤
5s ≤
4d ≤
5p ≤
6s ≤
2.1.2 Polyelectronic Atoms
4f ≤
5d ≤
6p ≤
7s ≤
5f ≤
6d
The Schrödinger equation for atoms with more than one (14)
electron cannot be solved analytically. If Ĥ
in equation (4) This sequence of orbital energies can be qualitatively
is neglected, Ĥ becomes separable in N one-electron opera- explained by considering the shielding of the nuclear charge
tors ĥi (p̂i , q̂i ) [ĥi (p̂i , q̂i )φ i (qi ) =
i φ i (qi )] (to simplify the by electrons in inner shells and the decrease, with increasing
notation, we use here and in the following the notation qi value of , of the penetrating character of the orbitals.
instead of qi to designate all spatial xi , yi , zi and spin msi When instantaneous correlation effects in the electronic
coordinates of the polyelectron wave function): motion are also considered, the wave functions depart
from a simple product form of the type of equation (12)


N and must be represented by a sum of configurations.
Ĥ0 = ĥi (p̂i , q̂i ) (11) One, therefore, says that electron correlation leads to
i=1 configuration mixing.
with eigenfunctions For most purposes and in many atoms, single-configur-
ation wave functions represent an adequate description,
Ψ k (q1 , . . . , qN ) = φ (k) (k) (k)
(12) or at least a useful starting point in the discussion of
1 (q1 )φ 2 (q2 ) . . . φ N (qN )
electronic structure and spectra. Equation (12) is, how-
and eigenvalues ever, not compatible with the generalized Pauli principle.
Indeed, electrons have a half-integer spin quantum num-
Ek =
1 +
2 + · · · +
N (13) ber (s = 1/2) and polyelectronic wave functions must be
antisymmetric with respect to the exchange (permutation)
where φ (k)
i (qi ) = Rn (ri )Ym (θ i , φ i )φ ms represents a spin of the coordinates of any pair of electrons. Equation (12)
orbital with φ ms being the spin part of the orbital, either α must, therefore, be antisymmetrized with respect to such
for ms = 1/2 or β for ms = −1/2. an exchange of coordinates. This is achieved by writing
 Fundamentals of Electronic Spectroscopy 183

the wave functions as determinants of the type: corresponding to the 36 entries of the table. Diagonal
elements of the table (designated by a cross) are forbidden
Ψ (q1 , . . . , qN ) by the Pauli principle because both electrons are in the
 
 φ 1 (q1 ) φ 1 (q2 ) . . . φ 1 (qN )  same spin orbital. According to equation (15), each pair of
 
 φ 2 (q1 ) φ 2 (q2 ) . . .  symmetric entries with respect to the diagonal can be used
 
1  .  to make one antisymmetric wave function. For example,
= √ det   (15)
 the entries of the table marked by an asterisk lead to the
N!  . 
 .  wave function
 
 φ (q1 ) ... . . . φ N (qN ) 
N
Ψ (q1 , q2 ) = (φ 2p0α (q1 )φ 2p1α (q2 )
in which all φ i are different spin orbitals. Such determinants √
− φ 2p1α (q1 )φ 2p0α (q2 ))/ 2 (16)
are called Slater determinants and represent suitable N -
electron wave functions that automatically fulfill the Pauli
which is antisymmetric with respect to permutation of q1
principle for fermions. Indeed, exchanging two columns in
and q2 and thus fulfills the generalized Pauli principle for
a determinant, i.e., permuting the coordinates of two elec-
fermions, and to one symmetric wave function
trons, automatically changes the sign of the determinant.
The determinant of a matrix with two identical rows is Ψ (q1 , q2 ) = (φ 2p0α (q1 )φ 2p1α (q2 )
zero so that equation (15) is also in accord with Pauli’s √
exclusion principle, namely, that any configuration with + φ 2p1α (q1 )φ 2p0α (q2 ))/ 2 (17)
two electrons in the same spin orbital is forbidden. This
is not surprising given that Pauli’s exclusion principle can which is forbidden by the Pauli principle. In total, there are
be regarded as a consequence of the generalized Pauli prin- 15 wave functions for the (2p)2 configuration that fulfill
ciple for fermions. The ground-state configuration of an the Pauli principle. Not all of these 15 wave functions
atom can thus be obtained by filling the orbitals in order correspond to states of the same energy.
of increasing energy (equation 14) with two electrons, one
with ms = 1/2 and the other with ms = −1/2, a procedure For an excited configuration with two unpaired electrons
known as Pauli’s Aufbau principle. such as He (1s)1 (2s)1 , the Pauli principle does not impose
any restriction, because the two electrons are in different
orbitals. However, the electrostatic repulsion between the
2.1.3 States of Different Spin Multiplicities with the two electrons leads to an energetic splitting of the possible
Example of Singlet and Triplet States states. In this configuration, four spin orbitals (1sα, 1sβ,
The generalized Pauli principle for fermions also restricts 2sα, and 2sβ) need to be considered, because each electron
the number of possible wave functions associated with a can be either in the 1s or in the 2s orbital with either ms =
given configuration, as illustrated with the ground electronic 1/2 or ms = −1/2. Four antisymmetrized functions fulfill-
configuration of the carbon atom in the following example. ing the Pauli principle result, which can be represented as
products of a symmetric/antisymmetric spatial part depend-
ing on the xi , yi , and zi coordinates of the two electrons
Example C(1s)2 (2s)2 (2p)2
(i = 1, 2) and an antisymmetric/symmetric spin part:
Because the full (1s)2 shell and the full (2s)2 subshell 
are totally symmetric, only the (2p)2 open subshell need 1
√ [1s(1)2s(2) − 1s(2)2s(1)] α(1)α(2) = Ψ T,MS =1
be considered. There are six spin orbitals and therefore 2
36(= 62 ) possible configurations (2pml ms )(2pm
l m
s ) with (18)
ml , m
l = 0, ±1 and ms , m
s = ±1/2:

Electron 1
φ 2p1α φ 2p1β φ 2p0α φ 2p0β φ 2p−1α φ 2p−1β
φ 2p1α x *
φ 2p1β x
Electron 2 φ 2p0α * x
φ 2p0β x
φ 2p−1α x
φ 2p−1β x
184 Fundamentals of Electronic Spectroscopy

 Table 4 Permutationally symmetric and antisymmetric two-

1
√ [1s(1)2s(2) − 1s(2)2s(1)] β(1)β(2) = Ψ T,MS =−1 electron spin functions.
2
(19) α(1)α(2) MS = 1
  Ψ S(s) (m1 , m2 ) √1 (α(1)β(2) + α(2)β(1)) MS = 0 S=1
1 1 2
√ [1s(1)2s(2) − 1s(2)2s(1)] √ [α(1)β(2) β(1)β(2) MS = −1 (triplet)
2 2
Ψ S(a) (m1 , m2 ) √1 (α(1)β(2) − α(2)β(1)) MS = 0 S=0
+ α(2)β(1)] = Ψ T,MS =0 (20) 2
(singlet)
 
1 1
√ [1s(1)2s(2) + 1s(2)2s(1)] √ [α(1)β(2)
2 2 Table 5 Permutationally symmetric and antisymmetric two-
− α(2)β(1)] = Ψ S,MS =0 (21) electron spatial functions.

Ψ R(s) (q1 , q2 ) √1 (φ 1 (1)φ 2 (2) + φ 1 (2)φ 2 (1)) (Singlet)

where the notation 1s(i)α(i) has been used to designate 2
Ψ R(a) (q1 , q2 ) √1 (φ 1 (1)φ 2 (2) − φ 1 (2)φ 2 (1)) (Triplet)
electron i being in the 1s orbital with spin projection 2
quantum number ms = 1/2.
The first three functions (equations 18, 19, and 20), with
MS = ms1 + ms2 = ±1, 0, have an antisymmetric spatial for the triplet state and as
part and a symmetric electron-spin part with respect to   
e2  1 
the permutation of the two electrons. These three functions 1s(1)2s(2) + 1s(2)2s(1)   1s(1)2s(2)
represent the three components of a triplet (S = 1) state. (8π
0 ) r12

The fourth function has a symmetric spatial and an anti-
+ 1s(2)2s(1) = J12 + K12 (23)
symmetric electron-spin part with MS = 0 and represents
a singlet (S = 0) state. These results are summarized in
Tables 4 and 5, where the spin parts of the wave functions for the singlet state. In equations (22) and (23), the integrals
are designated with a superscript “S” and the spatial parts J12 = J21 and K12 = K21 represent the so-called Coulomb
with a superscript “R”. The subscripts “a” and “s” indicate and exchange integrals, respectively. The Coulomb integral
whether the functions are symmetric or antisymmetric with can be interpreted as the energy arising from the repulsion
respect to the permutation of the coordinates of the two between the electron clouds of the 1s and 2s electrons.
electrons. The exchange integral is more difficult to interpret and
The contribution to the energy of the electron-repulsion results from the repulsion between the two electrons having
term Ĥ
= e2 /(4π
0 r12 ) in equation (4) can be evaluated “exchanged” their orbitals.
in the first order of perturbation theory as Because J12 and K12 are both positive in this case,
the triplet state lies lower in energy than the singlet
  
e2  1  state by twice the exchange integral. The energy splitting
1s(1)2s(2) − 1s(2)2s(1)   1s(1)2s(2) between the singlet and triplet states can, therefore, be for-
(8π
0 ) r12
 mally viewed as resulting from an electrostatic (including
exchange) coupling of the motion of the two electrons with
− 1s(2)2s(1)
spin vectors s1 and s2 , resulting in states of total spin angu-
    lar momentum S = s1 + s2 with S = 1 for the triplet state
e2  1  and S = 0 for the singlet state.
= 1s(1)2s(2)   1s(1)2s(2)
(8π
0 ) r12 These considerations can easily be generalized to situa-
    tions with more than two unpaired electrons. In atoms with
 1 
 
+ 1s(2)2s(1)   1s(2)2s(1) configurations with three unpaired electrons, such as N,
r12 (1s)2 (2s)2 (2p)3 , quartet (S = 3/2) and doublet (S = 1/2)
    states result.
 1 
 
− 1s(1)2s(2)   1s(2)2s(1)
r12
    2.1.4 Terms and Term Symbols in Atoms: LS and jj
 1  Coupling
− 1s(2)2s(1)   1s(1)2s(2)
r12 For all atoms extensive lists of term values are tabulated
= [J12 + J21 − K12 − K21 ]/2 (see, e.g., Moore 1949, 1952, 1958). To understand how the
different terms arise and derive the term symbols used to
= J12 − K12 (22) label them, it is necessary to understand how the different
 Fundamentals of Electronic Spectroscopy 185

orbital and spin angular momenta in an atom are coupled L. Then, the total electron spin S is determined by vectorial
by electromagnetic interactions and in which sequence the addition of the spins si of all electrons. Finally, the total
angular momentum vectors are added to form the total angular momentum J is determined by adding vectorially S
angular momentum vector J. This can be achieved by and L (Figure 5a). For a two-electron system, one obtains
ordering the different interactions according to their relative
strengths and by adding the angular momentum vectors that L =
1 +
2 , L = 1 + 2 , 1 + 2 − 1,
are most strongly coupled first.
. . . , |1 − 2 | (30)
Each angular momentum vector can be described quan-
tum mechanically by eigenvalue equations of the type of ML = m1 + m2 = −L, −L + 1, . . . , L (31)
equations (9) and (10), e.g.,
S = s1 + s2 , S = 1, 0 (32)
2
Ŝ |SMS  =
2 S(S + 1)|SMS  (24) MS = ms1 + ms2 = −S, −S + 1, . . . , S (33)

Ŝz |SMS  =
MS |SMS  (25) J = L + S, J = L + S, L + S − 1,

2
L̂ |LML  =
2 L(L + 1)|LML  (26) . . . , |L − S| (34)

L̂z |LML  =
ML |LML  (27) MJ = MS + ML = −J, −J + 1, . . . , J (35)

2
Ĵ |J MJ  =
2 J (J + 1)|J MJ  (28) The angular momentum quantum numbers L, S, and J
that arise in equations (30), (32), and (34) from the addi-
Jˆz |J MJ  =
MJ |J MJ  (29)
tion of the pairs of coupled vectors (
1 ,
2 ), (s1 , s2 ), and
(L, S), respectively, can be derived from angular momen-
In the absence of coupling between the different angular
tum algebra as explained in most quantum mechanics
momenta, all quantum numbers arising from eigenvalue
textbooks. For the addition of the angular momentum
equations of this type are good quantum numbers. In
vectors, the values of L resulting from the addition of
the presence of couplings between the different angular

1 and
2 can be obtained from the direct products of
momenta, however, only a subset of these quantum numbers
the corresponding representations of the Kh point group
remain good quantum numbers, and the actual subset
(Table 2). For instance, if 1 = 1 (irreducible represen-
of good quantum numbers depends on the hierarchy of
tation P) and 2 = 3 (irreducible representation F), the
coupling strengths (Zare 1988).
direct product P ⊗ F = D ⊕ F ⊕ G yields L = 2, 3, and 4,
Two limiting cases of angular momentum coupling
a result that can be generalized to equations (30), (32), and
hierarchy are used to label the terms of atoms: the LS
(34).
coupling hierarchy, which adequately describes the ground
The different terms (L, S, J ) that are obtained for the
state of almost all atoms except the heaviest ones and is
possible values of L, S, and J in equations (30), (32),
also widely used to label the electronically excited states
and (34) are written in compact form as term symbols:
of the lighter atoms, and the jj coupling hierarchy, which
is less frequently encountered but becomes important in
(L, S, J ) = 2S+1 LJ (36)
the description of the heaviest atoms and of electronically
excited states.
However, not all terms that are predicted by equations (30),
(32), and (34) are allowed by the Pauli principle. This
The LS Coupling Hierarchy
is best explained by deriving the possible terms of the C

L= N i=1
i strong coupling of orbital angular (1s)2 (2s)2 (2p)2 configuration in the following example.
momenta resulting from electrostatic
interactions Example C(1s)2 (2s)2 (2p)2

S= N s
i=1 i strong coupling of spins resulting from
Only the partially filled 2p subshell needs to be consid-
exchange terms in the electrostatic inter-
ered. In this case l1 = 1, l2 = 1 and s1 = s2 = 1/2. From
action (equations 22 and 23)
equations (30), (32), and (34) one obtains, neglecting the
J=L+S weaker coupling between S and L result-
Pauli principle,
ing from the spin–orbit interaction, a
relativistic effect.
L = 0(S), 1(P), 2(D)
In LS coupling, one obtains the possible terms by first
S = 0(singlet), 1(triplet)
adding vectorially the orbital angular momenta
i of the
electrons to form a resultant total orbital angular momentum J = 3, 2, 1, 0
186 Fundamentals of Electronic Spectroscopy

which leads to the following terms:

1 3 1 3 3 3 1 3 3 3
Term S0 S1 P1 P0 P1 P2 D2 D1 D2 D3
Degeneracy factor (gJ = 2J + 1) 1 3 3 1 3 5 5 3 5 7

Taking the (2J + 1) degeneracy factor of each term (which

corresponds to all possible values of MJ ), a total of empirical rules, known as Hund’s rules in honor of the
36 states results. As discussed above, only 15 states physicist Friedrich Hund. These rules state that
are allowed by the Pauli principle for the configuration 1. The lowest term is that with the highest value of the
(1s)2 (2s)2 (2p)2 . The terms allowed by the Pauli principle total spin angular momentum quantum number S.
can be determined by first finding the ML , MS , and MJ 2. If several terms have the same value of S, the term
values resulting from all 15 possible occupations of the with the highest value of the total angular momentum
six 2p spin orbitals with the two electrons in different spin quantum number L is lowest in energy.
orbitals, as explained in the following table: 3. If the lowest term is such that both L and S are
nonzero, the ground state is the term component with
El. 1 El. 2 ML MS MJ J = |L − S| if the partially filled subshell is less than
φ 2p1α φ 2p1β 2 0 2 half full, and the term component with J = L + S if
φ 2p0α 1 1 2 the partially filled subshell is more than half full.
φ 2p0β 1 0 1
φ 2p−1α 0 1 1 According to Hund’s rules, the ground state of C is the
φ 2p−1β 0 0 0 term component 3 P0 , and the ground state of F is the term
φ 2p1β φ 2p0α 1 0 1 component 2 P3/2 , in agreement with experimental results.
φ 2p0β 1 −1 0 Hund’s rules do not reliably predict the energetic ordering
φ 2p−1α 0 0 0 of electronically excited states.
φ 2p−1β 0 −1 −1 The energy level splittings of the components of a term
2S+1
φ 2p0α φ 2p0β 0 0 0 L can be described by considering the effect of the
φ 2p−1α −1 1 0 effective spin–orbit operator:
φ 2p−1β −1 0 −1
hcA
φ 2p0β φ 2p−1α −1 0 −1 ĤSO = L̂ · Ŝ (37)

2
φ 2p−1β −1 −1 −2
φ 2p−1α φ 2p−1β −2 0 −2 on the basis functions |LSJ  ( Ĵ = L̂ + Ŝ). In equation (37),
the spin–orbit coupling constant A is expressed in cm−1 .
2 2 2
The maximum value of ML is 2 and occurs only in From Ĵ = L̂ + Ŝ + 2L̂ · Ŝ, one finds
combination with MS = 0. This implies a 1 D term with five
MJ components corresponding to (ML MS ) = (2 0), (1 0), 1 2 2 2

L̂ · Ŝ = Ĵ − L̂ − Ŝ (38)
(0 0), (−1 0), and (−2 0). Eliminating these entries from 2
the table, the remaining entry with the highest ML value
has ML = 1 and comes in combination with a maximal The diagonal matrix elements of ĤSO , which represent
MS value of 1. We can conclude that the corresponding the first-order corrections to the energies in a perturbation
term is 3 P (consisting of 3 P0 , 3 P1 , and 3 P2 ). There are theory treatment, are
nine components corresponding to (ML MS ) = (1 1), (1
0), (1 −1), (0 1), (0 0), (0 −1), (−1 1), (−1 0), and
LSJ |ĤSO |LSJ 
(−1 −1). Eliminating these entries from the table, only 1
one component remains, (0 0), which corresponds to a 1 S0 = hcA[J (J + 1) − L(L + 1) − S(S + 1)] (39)
2
state. The terms corresponding to the (2p)2 configuration
allowed by the Pauli principle are therefore 1 D2 , 3 P2 , from which one sees that two components of a term with
3
P1 , 3 P0 , and 1 S0 . As in the case of the He (1s)1 (2s)1 J and J + 1 are separated in energy by hcA(J + 1). How-
configuration discussed above, the electrostatic exchange ever, one should bear in mind that first-order perturbation
interaction favors the triplet states over the singlet states. theory breaks down when the energetic spacing between
The lowest energy term of the ground electronic config- different terms is of the same order of magnitude as the
uration of almost all atoms can be predicted using three spin–orbit splittings calculated with equation (39). Hund’s
 Fundamentals of Electronic Spectroscopy 187

1S 1S MJ = 0 (32), and (34),

0
 
 1 
1000 –10 000 cm−1

1
(2nd row atoms)

2 j1 = l1 + s1 , j1 = l1 + , l1 − (40)
1D 1
1
2  2
D2 0
−1
−2 mj1 = ml1 + ms1 = −j1 , −j1 + 1, . . . , j1 (41)
2  
1 1  1 
3P
2 0
−1
j2 = l2 + s2 , j2 = l2 + , l2 −  (42)
−2
2 2
15 states
3 3P
1 mj2 = ml2 + ms2 = −j2 , −j2 + 1, . . . , j2 (43)
P 1 0
100 – −1
1000 cm−1 J = j1 + j2 , J = j1 + j2 , j1 + j2 − 1,
3P
Electrostatic
0 0
. . . , |j1 − j2 | (44)
Zeeman
interactions Spin – orbit
Orbital model
(orbit – orbit, interaction
effect in MJ = mj1 + mj2 = −J, −J + 1, . . . , J (45)
magnetic field
exchange)
The total orbital and spin angular momentum quantum
Figure 2 Schematic energy level structure of the (2p)2 configu- numbers L and S are no longer defined in jj coupling.
ration in LS coupling. Instead, the terms are now specified by a different set of
angular momentum quantum numbers: the total angular
third rule implies that the spin–orbit coupling constant A momentum ji of all electrons (index i) in partially filled
subshells and the total angular momentum quantum number
is positive in ground terms arising from less than half-full
J of the atom. A convenient way to label the terms
subshells and negative in ground terms arising from more
is (j1 , j2 , . . . , jN )J . Alternatively, the jj -coupling basis
than half-full subshells.
states may be written as
To illustrate the main conclusions of this section,
Figure 2 shows schematically by which interactions the 15
(j1 , j2 , . . . , jN )J = N
i=1 |ji , mji  (46)
states of the ground-state configuration of C can be split.
The strong electrostatic interactions (including exchange)
lead to a splitting into three terms 3 P, 1 D, and 1 S. The Example
weaker spin–orbit interaction splits the ground 3 P term The (np)1 ((n + 1)s)1 excited configuration:
into three components 3 P0 , 3 P1 , and 3 P2 . Each term LS coupling: S = 0, 1; L = 1. Term symbols: 1 P1 , 3 P0,1,2 ,
component can be further split into (2J + 1) MJ lev- which give rise to 12 states.
els by an external magnetic field, an effect known as jj coupling: l1 = 1, s1 = 12 , j1 = 12 , 32 and l2 = 0, s2 =
the Zeeman effect, which is discussed in more detail in
2 , j2 = 2 . Term symbols: [(j1 , j2 )J ] : ( 2 , 2 )0 ; ( 2 , 2 )1 ;
1 1 1 1 1 1
Section 2.1.7. ( 2 , 2 )1 ; ( 2 , 2 )2 , which also gives rise to 12 states.
3 1 3 1

The jj Coupling Hierarchy The evolution from LS coupling to jj coupling can

be observed by looking at the evolution of the energy
li + si = ji
 Strong spin–orbit coupling level structure associated with a given configuration as
ji = J Weaker electrostatic coupling. one moves down a column in the periodic table. Figure 3
illustrates schematically how the energy levels arising
In heavy atoms, relativistic effects become so large that the from the (np)1 ((n + 1)s)1 excited configuration are grouped
spin–orbit interaction can become comparable in strength, according to LS coupling for n = 2 and 3 (C and Si) and
or even larger, than the electrostatic (including exchange) according to jj coupling for n = 6 (Pb). The main splitting
interactions that are dominant in the lighter atoms. In between the (1/2, 1/2)0,1 and the (3/2, 1/2)1,2 states of Pb
jj coupling, the dominant interaction is the spin–orbit is actually much larger than the splitting between the 3 P and
coupling between li and si . The possible terms are obtained 1 P terms of C and Si. Figure 3 is the so-called correlation

by first adding vectorially the orbital angular momentum diagram, which represents how the energy level structure
vector li and the electron-spin vector si of each electron of a given system (here the states of the (np)1 ((n + 1)s)1
(index i) to form a resultant electronic angular momentum configuration) evolves as a function of one or more system
ji . The total electronic angular momentum J results from parameters (here the magnitude of the spin–orbit and
the vectorial addition of all ji . electrostatic interactions). States with the same values of
For a two-electron system, one obtains, using the same all good quantum numbers (here J ) are usually connected
angular momentum addition rules that led to equations (30), by lines and do not cross in a correlation diagram.
188 Fundamentals of Electronic Spectroscopy

J =1 (3/2, 1/2) E / (hc cm−1)

1P J=1 J=2

5000 1
(3/2, 1/2)
2
2

3P 1
1 1P 1 1 2
J=1 (1/2, 1/2) 1
0 2
J=0 J=0 3P 2
1
2
1
0 0 1
J 0
1st + 2nd row Pb
C, Si 1
0
Figure 3 Correlation diagram depicting schematically, and not
to scale, how the term values for the (np)((n + 1)s) configuration −5000
evolve from C, for which the LS coupling limit represents a good
description, to Pb, the level structure of which is more adequately
described by the jj coupling limit.
1 (1/2, 1/2)
0
The actual evolution of the energy level structure in the −10 000
series C, Si, Ge, Sn, and Pb, drawn to scale in Figure 4
C Si Ge Sn Pb
using reference data on atomic term values (Moore 1958),
enables one to see quantitatively the effects of the gradual Figure 4 Evolution from LS coupling to jj coupling with the
increase of the spin–orbit coupling. For the comparison, example of the term values of the (np)1 ((n + 1)s)1 configuration
the zero point of the energy scale was placed at the center of C, Si, Ge, Sn, and Pb. The term symbols are indicated without
of gravity of the energy level structure. In C, the spin–orbit the value of J on the left-hand side for the LS coupling limit and
interaction is weaker than the electrostatic interactions, on the right-hand side for the jj coupling limit. The values of
J are indicated next to the horizontal bars corresponding to the
and the spin–orbit splittings of the 3 P state are hardly positions of the energy levels.
recognizable on the scale of the figure. In Pb, it is stronger
than the electrostatic interactions and determines the main
splitting of the energy level structure. × 10−24 J T−1 is the Bohr magneton. By analogy, similar
equations can be derived for all other momenta. The
electron spin s and the nuclear spin I, for instance, give
2.1.5 Hyperfine Coupling rise to the magnetic moments:
Magnetic moments arise in systems of charged particles µB
with nonzero angular momenta to which they are propor- µ̂s = −ge γ ŝ = ge ŝ (49)


tional. In the case of the orbital angular momentum of
an electron, the origin of the magnetic moment can be and
understood by considering the similarity between the orbital
motion of an electron in an atom and a “classical” cur- µN
µ̂I = γ I Î = gI Î (50)
rent generated by an electron moving with velocity v in a

circular loop or radius r. The magnetic moment is equal to
respectively, where ge is the so-called g value of the elec-
e e tron (ge = −2.0023193043622(15)), γ I is the magneto-
µ=− r × me υ = −
= γ
(47) gyric ratio of the nucleus, µN = e
/(2mp ) = 5.05078324
2me 2me
(13) × 10−27 J T−1 is the nuclear magneton (mp is the mass
For the orbital motion of an electron in an atom, of the proton), and gI is the nuclear g factor (gp = 5.585
equation (47) can be written using the correspondence prin- for the proton). Because µN /µB = me /mp , the magnetic
ciple as moments resulting from the electronic orbital and spin
µ motions are typically 2–3 orders of magnitude larger than
µ̂ = γ
ˆ = − B
ˆ (48) the magnetic-dipole moments (and higher moments) of


nuclear spins.
where γ = −e/(2me ) represents the magnetogyric ratio of The hyperfine structure results from the interaction
the orbital motion and µB = e
/(2me ) = 9.27400915(23) between the magnetic moments of nuclear spins, electron
 Fundamentals of Electronic Spectroscopy 189

Jz Jz Jz Jz
J
I

J J
S hM F J
hMJ F F
S S
L L L
Jy Jy I Jy I Jy

Jx Jx Jx Jx
(a) (b)

Figure 5 (a) Schematic illustration of the vector model for the addition of two interacting angular momentum vectors with the example
of the LS coupling. The interacting vectors L and S precess around the axis defined by the resultant vector J, which has a well-defined
projection
MJ along the space-fixed z axis. (b) In the presence of a nuclear spin, the hyperfine interaction, which is typically much
weaker than the spin–orbit interaction, can be described as an interaction between J and I.

spins, and orbital angular momenta. The interaction between good approximation by
two angular momentum vectors (such as L̂ or Ŝ to form a
resulting angular momentum vector Ĵ (Section 2.1.4)) can J (J + 1) + S(S + 1) − L(L + 1)
gJ = 1 + (52)
be interpreted in the realm of a vector model (Zare 1988), 2J (J + 1)
based on a classical treatment and illustrated schematically
The hyperfine interaction results in a total angular momen-
in Figure 5(a) and (b). This vector model is used here to
tum vector F of norm |F|2 =
2 (F (F + 1)) and z-axis
discuss the hyperfine coupling.
projection
MF . The possible values of the quantum num-
The interaction between the two angular momentum
bers F and MF can be determined using the usual angular
vectors leads to a precession of both vectors around
momentum addition rules:
the axis defined by the resulting vector (J in the case
of the interaction of S and L), which is a constant F = |J − I |, |J − I | + 1, . . . , J + I (53)
of motion (see left-hand side of Figure 5a). Quantum
mechanically, this implies constant norms |L|2 =
2 L(L + and
1), |S|2 =
2 S(S + 1), and |J|2 =
2 J (J + 1) for L, S,
and J, respectively, and a constant component Jz =
MJ MF = −F, −F + 1, . . . , F (54)
along a quantization axis usually chosen as the z axis.
The projections of L and S along the z axis are no longer The hyperfine contribution to Ĥ arising from the interaction
defined, nor is the direction of J, except that the tip of the of µ̂J and µ̂I is one of the terms included in Ĥ

in
vector must lie on the dashed circle as shown on the right- equation (4) and is proportional to µ̂I · µ̂J , and thus to
hand side of Figure 5(a), which corresponds to a specific Î · Ĵ. Following the same argument as that used to derive
value of MJ . The possible values of the quantum numbers equation (39), one obtains
J and MJ that result from the addition of L and S are given
by equations (34) and (35). The larger the interaction, the 1 2 2 2

Î · Ĵ = F̂ − Î − Ĵ (55)
faster the precession of L and S around J. 2
The spin–orbit interaction is in general much stronger 2 2 2
than the interactions involving nuclear spins. On the with F̂ = Î + Ĵ and F̂ = Î + Ĵ + 2Î · Ĵ. The hyperfine
timescale of the slow precession of nuclear-spin vectors, energy shift of state |I J F  is therefore
the fast precession of L and S thus appears averaged out.    
 ha 
The hyperfine interaction can therefore be described as an  
I J F  2 Î · Ĵ I J F
interaction between I, with magnetic moment (gI µN /
)Î,

and J, with magnetic moment ha
= [F (F + 1) − I (I + 1) − J (J + 1)] (56)
2
µ̂J = gJ γĴ (51)
as can be derived from equation (55) and the eigenvalues of
2 2 2
rather than as two separate interactions of I with L and S F̂ , Î , and Ĵ . In equation (56), a is the hyperfine coupling
(Figure 5b). In equation (51), gJ is the g factor of the LS- constant in hertz. Note that choosing to express A in cm−1
coupled state, also called Landé g factor, and is given in and a in Hz is the reason for the additional factor of
190 Fundamentals of Electronic Spectroscopy

2P F+= 4
1/2
0.1925 cm−1

5370.27 cm−1
F+= 5
F = 1, M = 0, ±1
1s 2S1/2 83
Kr+ 2P
F+= 3 0.0161 cm−1
F+= 4
0.0475 cm−1 0.0298 cm−1
F+= 5
2P
3/2 0.0499 cm−1
F+= 6
(a) F = 0, M = 0 (b)

Figure 6 (a) Hyperfine structure of (a) the 1 2 S1/2 ground state of H. (b) The two spin–orbit components of the 2 PJ ground term of
Kr with J = 1/2, 3/2. [Adapted from Paul et al. 2009 and Schäfer and Merkt 2006.]

c in equation (37). As examples, we now briefly discuss in which ν̃ J is the position of the barycenter of the
the hyperfine structures of H (I = 1/2) and 83 Kr+ (I = hyperfine structure of the spin–orbit component with total
9/2). angular momentum quantum number J , and C = F (F +
For the H atom in the (1s)1 2 S1/2 ground state,  = 0 1) − I (I + 1) − J (J + 1). The second term on the right-
and µ̂J = µ̂S . The hyperfine interaction goes through direct hand side of the equation represents the splitting arising
contact of the electron and the nucleus, and is proportional from the magnetic-dipole interaction and is proportional to
to the electron probability density at the position of the the magnetic-dipole hyperfine coupling constant AJ . The
nucleus (r = 0), |Ψ (0)|2 = π1a 3 . This interaction is known third term is the next hyperfine coupling term in Ĥ

in
0
as Fermi-contact interaction and the value of the hyper- equation (4) and describes the electric-quadrupole hyperfine
fine coupling constant is a = 1420.4057517667(16) MHz interaction (Kopfermann 1958), which is proportional to the
(Essen et al. 1971). The hyperfine structure of the ground electric-quadrupole hyperfine coupling constant BJ . BJ is
state of H is depicted in Figure 6(a). The absolute ground zero for the upper spin–orbit component with J = 1/2.
state is, therefore, the F = 0, MF = 0 component of the Indeed dipole, quadrupole, octupole, etc. moments are
hyperfine doublet and is separated by only 1420 MHz nonzero only in systems with angular momentum quantum
(= 0.0475 cm−1 ) from the upper F = 1, MF = 0, ±1, lev- numbers J ≥ 1/2, 1, 3/2, . . . , respectively (Zare 1988).
els, which are degenerate in the absence of external fields. The octupole coupling in the 2 P3/2 state is negligible. The
This threefold degeneracy of the upper hyperfine com- values of the hyperfine coupling constants of the 2 P3/2
ponent is lifted in the presence of a magnetic field, as and 2 P1/2 components of the ground state of Kr+ are
explained in the following section. Because the electron A1/2 = −0.0385(5) cm−1 , A3/2 = −0.00661(3) cm−1 , and
density in the immediate vicinity of the nucleus scales B1/2 = −0.0154(7) cm−1 (Schäfer and Merkt 2006, Paul
as n−3 , the hyperfine splitting of excited members of the et al. 2009).
s Rydberg series can be obtained directly from that of
the ground state by dividing by n3 and rapidly becomes 2.1.6 Rydberg States
negligible. The hyperfine coupling constant in the ground
state of atomic hydrogen is almost the same as in the Rydberg states are electronic states in which one of the
ground state of ortho H2 + , because the 1σg orbital has electrons (called Rydberg electron) has been excited to a
hydrogenlike orbital having a principal quantum number
the form ( 1sa√+1s b
) and the electron density at each nucleus
2 n larger than the quantum number of the valence shell.
is to a good approximation half that of the H atom
The properties of these states can, therefore, be understood
(Section 2.2.1).
from the properties of the electronic states of the hydrogen
The . . . (4p)5 ground-state configuration of 83 Kr+ leads
atom described in Section 2.1.1. The expectation value
to two spin–orbit components 2 P3/2 and 2 P1/2 separated by
of the distance between the electron and the proton in
5370.27 cm−1 (Paul et al. 2009). The hyperfine structure is
the hydrogen atom increases as n2 , and the amplitude
well represented by equation (57):
of the Rydberg electron wave function in the immediate
vicinity of the proton decreases as n−3/2 so that, in a
AJ C polyelectronic atom, the electron density in the region of
ν̃(J, F ) = ν̃ J +
2 the positively charged core, where the Rydberg electron
3
4 C(C + 1) − I (I + 1)J (J + 1) interacts with the other electrons, decreases as n−3 . The
+ BJ (57) electron density in the core region also decreases rapidly
2I (2I − 1)J (2J − 1)
 Fundamentals of Electronic Spectroscopy 191

v+ = 1
N+ = 0

v+ = 0
v+ = 0 N+ = 2
v+ = 0 N+ = 1
N+ = 0
n=∞
Energy

n = 22
n = 20
n = 18
n = 16
n = 15
n = 14
n = 13

n = 12

n = 11
= 0, ..., n – 1 2 3, ..., n – 1
1
=0
(a) (b) (c)

Figure 7 Energy level structure of the Rydberg states of (a) the hydrogen atom, (b) polyelectronic atoms, and (c) molecules.

with the orbital angular momentum quantum number  converge on every rotational (denoted by N + in Figure 7),
because of the centrifugal barrier in the electron–ion-core vibrational (denoted by v + ), and electronic states of the
interaction potential, which is proportional to ( + 1). molecular cation. Because the potential that binds the Ryd-
Electronic states with a given value of  but different berg electron to the positively charged ion core can be well
values of n (n > ) form infinite series of electronic approximated by a Coulomb potential, the Rydberg elec-
states known as Rydberg series. The energetic positions of tron wave functions in polyelectronic atoms and molecules
the different members of a given Rydberg series can be are hydrogenlike and can be labeled by the same quantum
described in good approximation by the Rydberg formula: numbers.
Most properties of Rydberg states scale as integer powers
hcRM of the principal quantum number, as summarized in Table 6,
Enm = EI (α + ) − (58)
(n − δ )2 so that Rydberg states of high principal quantum number
behave very differently from other electronic states. The
where EI (α + ) represents the energy of a given quantum scaling laws in Table 6 can be derived from the well-
state α + of the ionized atom (or molecule) and δ is the so- known properties of the eigenstates of the hydrogen atom
called quantum defect, which is to a good approximation (Gallagher 1994, Bethe and Salpeter 1957).
constant in a given series. δ only appreciably differs from Properties of particular relevance for electronic spec-
zero in s, p, and d Rydberg states and rapidly decreases troscopy are (i) the very long lifetimes of high Rydberg
with increasing  value. states (the lifetimes scale as n3 ), which result in very nar-
Figure 7 depicts the energy level structure characteris- row spectral lines; (ii) the absorption cross sections from
tic of Rydberg states of the hydrogen atom (a), polyelec- the ground or a low-lying electronic state, which decrease
tronic atoms (b), and molecules (c) at high n values. In very rapidly with n (as n−3 ) and make high Rydberg states
polyelectronic atoms, the energy level structure resembles difficult to observe in single-photon absorption spectra from
closely that of the hydrogen atom with the only excep- the ground state; (iii) the fine-structure (e.g., from the
tion that the low- states are displaced to lower energies spin–orbit interaction) and hyperfine-structure (e.g., from
because the Rydberg electron is exposed to an increasing the Fermi-contact interaction) splittings involving the Ryd-
nuclear charge when it penetrates through the inner elec- berg electron, which are proportional to the Rydberg elec-
tron shells (their quantum defect is positive). In molecules, tron density in the core region, i.e., to n−3 , and become
the situation is additionally complicated by the fact that negligible at high n values; (iv) the spacings between neigh-
core-penetrating and core-nonpenetrating Rydberg series boring Rydberg states of a given series, which also decrease
192 Fundamentals of Electronic Spectroscopy

Table 6 Properties of Rydberg atoms(a) .

Property n dependence Na(10d)(b) H(100d)

Binding energy n−2 1100 cm−1 11 cm−1

Energy between adjacent n states n−3 190 cm−1 0.22 cm−1
Threshold ionization field n−4 33 kV cm−1 3.3 V cm−1
Orbital radius n2 147 a0 1.50 × 104 a0
Geometric cross section n4 6.8 × 104 a02 7.1 × 108 a02
Dipole moment
n|er|n( + 1) n2 143 ea0 1.50 × 104 ea0
Polarizability n7 0.21 MHz cm2 V−2 2 × 106 MHz cm2 V−2
(c)
Radiative lifetime n3 1.0 µs 0.53 ms(d)
(a)
Atomic units: Bohr radius a0 = 0.5292 × 10−10 m; dipole moment ea0 = 8.478 × 10−30 C m = 2.542 D.
(b)
From Gallagher (1988).
(c)
In the presence of electric fields the lifetimes scale as n4 and if the electric fields are inhomogeneous even as n5 (Merkt 1997).
(d)
Extrapolated from the values given by Lindgård and Nielsen (1977).

as n−3 and make it difficult to spectrally resolve adjacent and the magnetic moment originates from the orbital motion
members of a Rydberg series at high n values; (v) the very of the electrons (equation 48):
high sensitivity to electric and magnetic fields (the polariz-
µB
ability scales as n7 ); and (vi) the binding energies, which µ̂m,z = − L̂z (60)


decrease as n−2 and vanish at n = ∞ and make it possi-
ble to derive precise ionization energies and ionic energy In first-order perturbation theory, the energy shift caused by
levels by extrapolation of the Rydberg series. The articles the magnetic field is, according to equations (59) and (60),
Jungen 2011a: Elements of Quantum Defect Theory and given by
Jungen 2011b: Ab Initio Calculations for Rydberg States
of this handbook are specifically devoted to Rydberg states, ∆E = −µm,z B = µB BML (61)
and the article Merkt et al. 2011: High-resolution Photo-
electron Spectroscopy, this handbook illustrates the use of A given term with L = J thus splits into 2L + 1 magnetic
high Rydberg state in high-resolution photoelectron spec- sublevels corresponding to the possible ML values. The
troscopy. energy separation of two sublevels differing in ML by
1 is simply µB B, grows linearly with B and depends
2.1.7 Atoms in Magnetic Fields neither on the atom nor on the state of the atom under
consideration. The normal Zeeman effect on the energy
In the presence of a magnetic field, an additional term, level structure of 1 S, 1 P, and 1 D terms is illustrated in
Figure 8. Particularly simple spectra result, as discussed
−µ̂m · B (59) in Section 3.2.3. The normal Zeeman effect is primarily
used to unambiguously distinguish S = 0 from S = 0 terms
arises in the Hamiltonian of a system having a magnetic
moment µm . In the case of a homogeneous magnetic field
4
B = (0, 0, B) applied along the z axis of the laboratory
frame, this term simplifies to −µ̂z B and induces energy 3 ML = 3
shifts and/or lifts the degeneracy of the magnetic sublevels. 2 ML = 2
The effect of a magnetic field on the spectrum of an atom 1 ML = 1
E / (µB B )

or a molecule is called the Zeeman effect, the physicist P.

0 ML = 0
Zeeman being the first to observe it as a broadening in
the spectra of atoms. This section summarizes the main −1 M L = −1
aspects of the Zeeman effect on the energy levels of −2 M L = −2
atoms. −3 M L = −3

−4
The Normal Zeeman Effect The simplest situation is 1S 1P 1D 1F

that of an atom with S = 0, for which the effect of the

magnetic field is referred to as the normal Zeeman effect Figure 8 The normal Zeeman effect on the energy level struc-
for historical reasons. In this case, J = L and MJ = ML , ture of (a) 1 S, (b) 1 P, (c) 1 D, and (d) 1 F terms.
 Fundamentals of Electronic Spectroscopy 193

Jz Jz

hMI
I

hMS
S hMF J
hMJ hMJ
S
hML
L L
Jy Jy

(a) Jx (b) Jx

Figure 9 Vector model illustrations of (a) the Paschen–Back effect and (b) the nuclear Paschen–Back effect.

and can also be used to measure magnetic field strengths, absence of magnetic field. Consequently, the spin–orbit
the value of the Bohr magneton being known with high interaction can be described as taking place between the
precision (see above). “averaged” spin and orbital angular momentum vectors,
i.e., their z components, as is illustrated by Figure 9(a). The
The Anomalous Zeeman Effect When S = 0, the com- corresponding operator (equation 37) can be approximated
ponent of the magnetic moment along the field axis (taken by (2πc/
)AL̂z Ŝz . In this high-field limit, the Zeeman level
here as the z axis) is given by shifts ∆E can be described by
µB ˆ ∆E = µB B(ML − ge MS ) + hcAML MS (64)
µ̂m,z = −gJ Jz (62)


The Paschen–Back effect is only observable in atoms
and the energy levels are shifted by
subject to a particularly weak spin–orbit interaction or
at extremely large magnetic field strengths. Below 1 T,
∆E = gJ µB BMJ (63)
the anomalous Zeeman effect discussed above is typi-
cally observed. The anomalous Zeeman and Paschen–Back
The shifts and splittings of the energy levels now depend
effects can thus be recognized as low- and high-field limits
on the state under investigation through the dependence of
of the interaction between LS coupled states and mag-
gJ on S, L, and J (equation 52). The anomalous Zeeman
netic fields. The treatment of intermediate cases leads
effect thus leads to more complex spectra than the normal
to more complicated energy level patterns than pre-
Zeeman effect (Section 3.2.3), and the observed splittings
dicted by equations (63) and (64). An effect similar to the
permit the unambiguous determination of the term symbols.
Paschen–Back effect can also be observed in electric fields
In the early part of the twentieth century, the interpretation
and, indeed, the electronic angular momentum coupling
of the anomalous Zeeman effect represented a real puzzle
scheme for diatomic molecules discussed as case (a) in
and played an important role in the discovery of the electron
Section 2.2.5 can be regarded as a Paschen–Back effect
spin (Enz 2002). Today, the distinction between normal
induced by the electric field along the internuclear axis of
and anomalous Zeeman effect seems artificial because
a diatomic molecule.
the normal Zeeman effect is merely a special case of
equation (63) for S = 0 and gJ = 1. The Nuclear Paschen–Back Effect The hyperfine inter-
action being much weaker than the spin–orbit interaction,
The Paschen–Back Effect In the limit of very high even moderate magnetic fields lead to precessions of J and
magnetic field strength, the interaction of the magnetic I around the axis determined by the field vector that are
moments µ̂S and µ̂L of a state subject to LS coupling faster than that of J and I around F (Figure 9b). In this
at zero magnetic field strength with the magnetic field case, referred to as the nuclear Paschen–Back effect, the
becomes stronger than the spin–orbit interaction. This effect of the magnetic field on the hyperfine structure can
situation is know as the Paschen–Back effect. In terms of be described as
the vector model discussed in the context of Figure 5, this
limit implies that the precession of L and S around the ∆E = B(µB gJ MJ − µN gI MI ) + haMJ MI (65)
axis determined by the magnetic field vector (i.e., the z
axis of the laboratory frame) is faster than that of L and S The nuclear Paschen–Back effect is usually encountered
around the axis determined by the direction of J in the at field strengths large enough to resolve the nuclear
194 Fundamentals of Electronic Spectroscopy

E the field is applied along the z axis (E = (0, 0, E)), the

(GHz)
h term eEz = eEr cos θ has to be added to the Hamiltonian
10 operator which becomes
MF = 1

2 2 e2
MF = 0 Ĥ = − ∇e − + eEr cos θ = Ĥo + Ĥ
(66)
2me 4π
0 r
F = 1 and MF = 0, ±1
At low field strength, the effect of the electric field can
F = 0 and MF = 0
be treated adequately with first-order perturbation theory
MF = −1 for degenerate states. The matrix elements of Ĥ
in the
|nm basis (we use m instead of m to simplify the
MF = 0 notation) can be written as
n

m
|Er cos θ |nm. These
−10
elements can be expressed as products of radial and angular
matrix elements E
n

|r|n

m
| cos θ |m and imply the
perturbation selection rules:
0.0 0.2 0.4 0.6 0.8 1.0

∆m = m
− m = 0, ∆ = 
−  = ±1,
B/T

Figure 10 The hyperfine structure of the H atom in its 2 S1/2 ∆n = 0, ±1, ±2, . . . (67)
ground state and its dependence on the magnetic field.
The ∆ selection rule can be derived using Tables 1 and 2
Zeeman effect in electronic spectra. As a simple illustration, if one uses the fact that z = r cos θ transforms as the
Figure 10 shows the evolution of the hyperfine structure irreducible represention Pu of the Kh point group. The
of the H atom with the magnetic field. At field strengths selection rule of the magnetic quantum number can be
beyond ≈ 1 T, the energy level pattern reveals a main rationalized by the fact that m remains a good quantum
splitting arising from the first term of equation (65) with number in cylindrical symmetry. Because of the degenerate
MJ = MS = ms and gJ = −ge ≈ 2. Each of the two groups nature of all |nm states having the same n value in
of ms levels is further split by the other two terms. After the hydrogen atom at zero field, the perturbation leads
Figure 3, which illustrated the evolution from LS to jj to a linear splitting of the degenerate energy levels (the
coupling, Figure (10) is a second example of a correlation linear Stark effect) represented in Figure 11(a) for n = 5.
diagram and shows how the energy level structure of the The electric field breaks the central symmetry, so that the
(1s)1 2 S1/2 ground state of H evolves from the situation orbital angular momentum quantum number  ceases to be
described by equation (56) and depicted in Figure 6(a) at a good quantum number. Instead, states of different angular
B = 0 to that described by equation (65) at B = 1 T. In the momentum quantum number  but the same values of m
presence of a homogeneous magnetic field, the anisotropy are mixed by the electric field. The atoms are polarized by
of free space is broken, and even F ceases to be a good the electric field, as illustrated in Figure 11(b), in which
quantum number. The only good quantum number that can the electron density in a plane containing the z axis is
be used as a label for the states through the entire diagram displayed for the five m = 0 levels. The energy levels
is MF . are more easily expressed as a function of the so-called
parabolic quantum numbers n1 and n2 that arise from
2.1.8 Atoms in Electric Fields the solution of Schrödinger equation of the H atom in
parabolic coordinates (Gallagher 1994) than as a function of
Atomic energy levels are also affected by electric fields , because the |nn1 n2 m basis functions are adapted to the
and the resulting energy shifts and splittings are referred cylindrical symmetry of the problem. The quantum numbers
to as the Stark effect. The effect of the electric fields is n1 and n2 can each take the values between 0 and n − 1.
particularly pronounced in Rydberg states, which are highly In atomic units, the energy levels are given to first order of
polarizable (the polarizability scales as n7 , see Table 6). perturbation theory by
The primary effect of an electric field is to couple energy
levels from configurations differing by one spin orbital 1 3
only, with the additional restriction that the coupled spin Enn1 n2 m = − + (n1 − n2 )nE (68)
2n2 2
orbitals should only differ by one unit of the orbital
angular momentum quantum number . The hydrogen and depend linearly on the field strength. One thus speaks
atom represents a very special case because all orbitals of of the linear Stark effect. To label the states, it is useful
the same principal quantum number n are degenerate. If to use the difference k between n1 and n2 . For given
 Fundamentals of Electronic Spectroscopy 195

−50
k m −25
x /a 0
0
25
50
4 0
50
0 25
−50 −25 z /a
0
Energy

3 ±1
−50
−25
x /a 0
0
25
2 0, ±2 50
50
0 25
−50 −25 z /a
0
1 ±1, ±3
−50
−25
x /a 0
0
n=5 0 0, ±2, ±4 25
50
50
0 25
−50 −25 z /a
0
−1 ±1, ±3
−50
−25
x /a 0
0
−2 0, ±2 25
50
50
0 25
−50 −25 z /a
−3 ±1 0

−50
−25
x /a 0
0
−4 0 25
50
50
0 25
(a) Electric field strength (b) −50 −25 z /a
0

Figure 11 The linear Stark effect in the n = 5 state of atomic hydrogen. (a) Energy level diagram and (b) electron density in the xz
plane of the m = 0 states. The position of the nucleus is at the origin of the coordinate system. k represents the difference n1 − n2 .

values of n and |m|, k takes values ranging from −(n − Table 7 Character table of the C∞v point group.
|m| − 1) to (n − |m| − 1) in steps of 2 (Figure 11a). The
plots of the electron density represented in Figure 11(b) C∞v E 2Cϕ∞ . . . ∞σv
enable one to see that all states except the k = 0 states
+ (= A1 ) 1 1 . . . 1 z x 2 + y 2 , z2
have electric-dipole moments and to understand why the − (= A2 ) 1 1 . . . −1 Rz
states with a positive value of k are shifted to higher (= E1 ) 2 2 cos ϕ . . . 0 x, y; Rx , Ry xz, yz
energies by the field, whereas those with a negative value ∆(= E2 ) 2 2 cos 2ϕ . . . 0 x 2 − y 2 , xy
of k are shifted to lower energies. Equation (68) can be (= E3 ) 2 2 cos 3ϕ . . . 0
converted to SI units using the fact that the ratio between ... ... ... . . . ...
the atomic unit of energy and the atomic unit of electric
field is ea0 with e = 1.602176487(40) × 10−19 C and a0 =
5.2917720859(36) × 10−11 m: In polyelectronic atoms, the levels that can be coupled by
hcRH 3 the electric field are nondegenerate and the Stark effect
Enn1 n2 m = − + ea0 (n1 − n2 )nE (69) is quadratic, i.e., the energies depend quadratically on
n2 2
E, as is expected from second-order perturbation the-
Expressing the positions in the spectroscopic unit of cm−1 , ory. However, nonpenetrating Rydberg states, which are
one obtains degenerate at zero field (Figure 7), represent an exception
to this behavior, and behave very similarly in an elec-
RH /cm−1 tric field to the states of the hydrogen atom. Stark spec-
ν̃ nn1 n2 m /cm−1 = − + 6.40215 × 10−5
n2 tra of Ar Rydberg states are discussed in Section 3.2.3
× (n1 − n2 )n(E/(V cm−1 )) (70) (Figure 41).
196 Fundamentals of Electronic Spectroscopy

Table 8 Character table of the D∞h point group.

ϕ ϕ
D∞h E 2C∞ ... ∞σv i 2S∞ ... ∞ C2

+
g 1 1 . . . 1 1 1 . . . 1 x 2 + y 2 , z2
−
g 1 1 . . . −1 1 1 . . . −1 Rz
g 2 2 cos ϕ . . . 0 2 −2 cos ϕ . . . 0 Rx , Ry xz, yz
∆g 2 2 cos 2ϕ . . . 0 2 2 cos 2ϕ . . . 0 x 2 − y 2 , xy
... ... ... . . . ... ... ... . . . ...
+
u 1 1 . . . 1 −1 −1 . . . −1 z
−
u 1 1 . . . −1 −1 −1 . . . 1
u 2 2 cos ϕ . . . 0 −2 2 cos ϕ . . . 0 x, y
∆u 2 2 cos 2ϕ . . . 0 −2 −2 cos 2ϕ . . . 0
... ... ... . . . ... ... ... . . . ...

Table 9 Direct-product table of the point groups C∞v and D∞h . quantity in a spherically symmetric potential. L and  are
therefore good quantum numbers in atoms (Section 2.1).
In diatomic molecules, the symmetry of the potential is
× + − ∆  ...
reduced to cylindrical symmetry, so that only the projection
+ + − ∆  . . . of the total orbital angular momentum onto the internu-
− + ∆  . . . clear axis is conserved as long as spin–orbit coupling can
+, −, ∆ ,  ∆,  . . . be neglected. The irreducible representations σ, π, δ, . . .
∆ +, −,  , H . . .
correspond to orbitals with values of 0, 1, 2, . . . of the
 +, −, I . . .
... ... ... ... ... ... . . . orbital angular momentum projection quantum number λ
on the internuclear axis. Similarly, , , ∆, . . . are used
For D∞h : g × g = u × u = g and g × u = u × g = u. to label electronic states with total orbital angular momen-
tum projection quantum number Λ = 0, 1, 2, . . . on the
2.2 Diatomic Molecules internuclear axis, respectively. Orbitals of σ− symmetry do
not exist because no σ molecular orbital can be formed that
Homonuclear diatomic molecules (H2 , N2 , . . .) and het- has a nodal plane containing the internuclear axis, but elec-
eronuclear diatomic molecules (NO, HCl, . . .) belong to tronic states of − symmetry result from configurations in
the D∞h and C∞v point groups, respectively. The charac- which at least two orbitals of symmetry π, or δ, or φ, . . .
ter tables of these point groups are given in Tables 7 and 8, are singly occupied (see Tables 7, 8, 9, and 10).
and the corresponding product table is presented in Table 9. How the quantum number λ arises in a linear molecule
The orbitals and electronic states of molecules are labeled can also be understood by writing the Schrödinger equation
σ , π, δ, . . . and + , − , , ∆, . . ., respectively, accord-
+ for a single electron in an axially symmetric potential in
ing to the irreducible representations of the corresponding cylindrical coordinates:
point groups. Nondegenerate orbitals (or states) belong
to one-dimensional irreducible representations (σ ( )), ∂ 2Ψ ∂ 2Ψ 1 ∂Ψ 1 ∂ 2Ψ 8π2 m
+ + + + (E − V )Ψ = 0
whereas doubly degenerate orbitals (or states) belong to ∂z2 ∂ρ 2 ρ ∂ρ ρ 2 ∂ϕ 2 h
two-dimensional irreducible representations (π ( ), δ (∆), (71)
φ (), . . .). where z is the coordinate of the electron along the symmetry
The symmetry labels of molecular orbitals and electronic axis, ρ its distance from the axis, and ϕ the azimuthal angle.
states of diatomic molecules are determined using the same Inserting the ansatz
procedure as for atoms: molecular orbitals are designated
by lower-case Greek letters (σ+ , π, δ, . . . for heteronuclear Ψ (z, ρ, ϕ) = χ (z, ρ)f (ϕ) (72)
diatomic molecules and σg+ , σu , πg , πu , . . . for homonu-
clear diatomic molecules). Electronic states are designated in equation (71) and multiplying the equation with ρ 2 /Ψ
by capital Greek letters ( + , − , , ∆, . . . for heteronu- gives
clear diatomic molecules and + − + −
g , g , u , u , g , u ,
ρ2 ∂ 2χ ρ 2 ∂ 2χ ρ ∂χ 8π2 mρ 2
. . . for homonuclear diatomic molecules). As in atoms, + + + (E − V (z, ρ))
the symmetry labels also contain information on the elec- χ ∂z2 χ ∂ρ 2 χ ∂ρ h
tronic angular momentum. In the absence of spin–orbit 1 ∂ 2f
coupling, the orbital angular momentum is a conserved =− (73)
f ∂ϕ 2
 Fundamentals of Electronic Spectroscopy 197

Table 10 Terms belonging to the most frequent electronic configurations of diatomic molecules.

Config. Terms Config. Terms

σ2 1 + π2 σδ 1 + , 1 − , 1 ∆(2), 1 , 3 + , 3 − , 3 ∆(3),
3 , 5 ∆

π2 1 +, 3 −, 1∆ π2 ππ 1 + (3), 1 − (3), 1 ∆(4), 1 , 3 + (4),

3 − (4), 3 ∆(5), 3 , 5 + , 5 − , 5 ∆

π3 2
i π2 π2 1
+ (3), 1 − , 1 ∆(2), 1 , 3 + (2)
3 − (2), 3 ∆(2), 5 +

π4 1 + π3 σ 1 , 3
i
δ2 1 +, 3 −, 1 π3 π 1 + , 1 − , 1 ∆, 3 + , 3 − , 3 ∆

δ3 2
∆i π3 δ(π3 δ3 ) 1
, 1 , 3 , 3 
δ4 1 + π3 σσ 2 (2), 4

π2 σ 2 + , 2 − , 2 ∆, 4 − π3 π2 2 , 2 (2), 2  , 4
i i i
π2 π 2 , 2 (2), 2 , 4 π3 π3 1 + , 1 − , 1 ∆, 3 + , 3 − , 3 ∆
i i
π2 δ 2 + , 2 − , 2 ∆, 2 ∆ , 2 , 4 ∆ π3 π2 σ 1 (3), 1 , 3 (2), 3 (2), 3  , 5
i i i i
1 + 1 − 1
π2 σσ , , ∆, , (2), 3 ∆, 5 −
3 + 3 −
π3 π3 σ 2 +
(2), 2 − (2), 2 ∆, 2 ∆i , 4 + , 4 − , 4 ∆i
π2 σπ 1 (3), 1 , 3 (2), 3 (2), 3 , 5
i

The index i designates inverted term multiplets. The g and u labels relevant for homonuclear diatomic molecules can be determined from the number
N of electrons in MO orbitals of u symmetry. When N is gerade, the terms are g; otherwise, they are u.

Equating both sides to a constant λ2 , one obtains the

+ −
differential equation in ϕ 2p + −
+ +
su1s
∂ 2 f (ϕ)
+ λ2 f (ϕ) = 0 (74) 1s 1s
∂ϕ 2
sg1s
which has the solutions
+
f± (ϕ) = e±iλϕ (75)
1s
Because f (ϕ) = f (ϕ + 2π), λ must be an integer number. +
The general solution of equation (71) is therefore
Figure 12 Correlation diagram from the two 1s atomic orbitals
Ψ ± (z, ρ, ϕ) = χ(z, ρ)e±iλϕ (76) of two identical separated atoms to the 1s and 2pz orbitals of
the corresponding united atom through the σg+ and σu+ molecular
Since the Ψ ± are energetically degenerate (the ±λ solutions orbitals.
have identical eigenvalues), an arbitrary linear combination
is also a solution. The Ψ ± have a well-defined value of λ,
but their linear combination does not. The labels σ, π, δ, at an infinite internuclear separation. Molecular states are
. . . give the absolute value of λ. formed by progressively approaching the atoms toward the
equilibrium internuclear separation. The expected form and
energetic order of the molecular orbitals can be predicted
2.2.1 Molecular Orbitals by linking the two limiting cases in a correlation diagram
In the qualitative representation of molecular orbitals, it by making sure that curves of the same symmetry do not
is helpful to discuss two extreme situations: the united- cross. Figure 12 shows how the two 1s atomic orbitals of
atom limit and the separated-atom limit. In the united-atom the two separated H atoms correlate through the σg+ and
limit, the atoms that form the molecule are considered to σu+ molecular orbitals with the 1s and 2pz orbitals of the
have coalesced into a single atom. The united-atom lim- united atoms. By convention, the z axis is chosen to be
its of 16 O2 and H2 are 32 S and 2 He, respectively. The the internuclear axis. Figures 13 and 14 display the corre-
molecular structure is determined by progressively sepa- lation diagrams connecting the energy levels of the sepa-
rating the atomic components of the molecule toward the rated atoms with those of the united atoms in the case of
equilibrium internuclear separation. In the limit of the sepa- homonuclear and heteronuclear diatomic molecules, respec-
rated atoms, the atoms forming the molecule are considered tively. Different molecules with their specific internuclear
198 Fundamentals of Electronic Spectroscopy

4d d 3d
4d
4d p
4d s su 3p
4p 4p p pg 3p 3p
4s 4p s pu 3p
4s s sg 3p
3d 3d d su 3s 3s
3d p sg 3s
3d s
3p 3p p su 2p
3p s pg 2p 2p
3s pu 2p
3s s su 2p
su 2s
sg 2s
2s
2p 2p p
2p s
2s
2s s

su 1s
1s
sg 1s

Li2N2
1s 1s s R
H2

Figure 13 Correlation diagram illustrating the evolution of molecular orbitals between the separated-atoms limit (right) and the
united-atoms limit (left) for homonuclear diatomic molecules. [Adapted from Herzberg (1989).]

separation occupy different positions along the horizontal ordering of the orbitals is
axis of these figures.
The determination of molecular orbitals often relies on 1σg (1s) < 1σu∗ (1s) < 2σg (2s) < 2σu∗ (2s) < 1πu (2p)
the LCAO (linear combinations of atomic orbitals) method. < 3σg (2p) < 1π∗g (2p) < 3σu∗ (2p) (78)
Molecular orbitals φ j are formed from symmetry-adapted
linear combinations of atomic orbitals ϕ i following In the case of O2 + , O2 , O2 − , F2 + , F2 , F2 − , and Ne2 + , it is

1σg (1s) < 1σu∗ (1s) < 2σg (2s) < 2σu∗ (2s) < 3σg (2p)
φj = cj i ϕ i (77)
i < 1πu (2p) < 1π∗g (2p) < 3σu∗ (2p) (79)

Several conditions must be fulfilled to form molecular These two cases are depicted schematically in Figure 15(b)
orbitals that are distinct from the original atomic orbitals: and (c), respectively.

• The energies of the atomic orbitals that are combined

2.2.2 Electronic Configurations
must be similar. Electronic configurations are obtained by filling the spatial
• The atomic orbitals must overlap at the equilibrium orbitals according to the Pauli principle with no more than
internuclear separation. two electrons. The ground-state configuration of N2 , e.g.,
• The atomic orbitals must be symmetry compatible. is

(1σg )2 (1σu∗ )2 (2σg )2 (2σu∗ )2 (1πu )4 (3σg )2 (80)

Figure 15(a) shows the structure of molecular orbitals
of homonuclear diatomic molecules consisting of atoms and the first two excited configurations are
of the second row of the periodic system. For Li2 + , Li2 ,
Li2 − , B2 + , B2 , B2 − , C2 + , C2 , C2 − , and N2 + , the energetic (1σg )2 (1σu∗ )2 (2σg )2 (2σu∗ )2 (1πu )4 (3σg )1 (1π∗g )1 (81)
 Fundamentals of Electronic Spectroscopy 199

4d 4d d
4d p 3dB
4d s 3dA
4p 4p p p 3pB
4p s s 3pB 3pB
4s
4s s p 3pA 3pA
3d 3d d s 3pA 3sB
3d p s 3sB
3sA
3d s s 3sA
3p 3p p p 2pB 2pB
3p s s 2pB
3s 2pA
3s s p 2pA
s 2pA 2sB
s 2sB
2sA
2p 2p p s 2sA
2p s
2s
2s s

1sB
s 1sB

1sA
s 1sA

CO
1s 1s s
R
CH

Figure 14 Correlation diagram between separated atoms (right) and united atoms (left) for heteronuclear diatomic molecules. [Adapted
from Herzberg (1989).]

and orbitals need to be considered, because full shells and sub-

shells are totally symmetric (1 + 1 +
g and for homonuclear
(1σg )2 (1σu∗ )2 (2σg )2 (2σu∗ )2 (1πu )3 (3σg )2 (1π∗g )1 (82) and heteronuclear diatomic molecules, respectively). The
character  of the spatial part of the electronic term is
The ground-state configuration of O2 is determined from the direct product (see Table 9) of the
irreducible representations
(1σg )2 (1σu∗ )2 (2σg )2 (2σu∗ )2 (3σg )2 (1πu )4 (1π∗g )2 (83)
 = (f (qi )) ⊗ (f (qj )) ⊗ . . . (84)
If two electrons are located in the same spatial orbital,
they must have opposite spins. As in the case of atoms, of the molecular orbitals, where the product extends over
an electronic configuration leads in general to several all electrons in partially filled molecular orbitals.
electronic terms and several electronic states. Applying equation (84) to the configurations (80)–(83),
one can draw the following conclusions:
2.2.3 Electronic Wave Functions and Electronic 1. Since all orbitals of the configuration (80) are fully
Terms occupied, the totally symmetric representation + g
As explained in Section 2.1.2, N -electron wave functions results. Moreover, because all electrons are paired, a
Ψ (q1 , q2 , . . . , qN ) of molecules must obey the generalized unique singlet term of symmetry 1 + g is obtained.
Pauli principle. Consequently, they must be antisymmet- Consequently, the ground electronic state of N2 is
ric under the pairwise permutation of electrons, which is designated as X 1 + g.
automatically fulfilled by Slater determinants of the gen- 2. The (3σg )1 (1π∗g )1 part of configuration (81) leads to
eral form given by equation (15). The spatial part of the a g term. The corresponding spin multiplicities are
one-electron functions φ i corresponds to a molecular orbital derived in Section 2.2.4.
of the form (76) and (77). To determine the possible elec- 3. Because (1πu )3 can be considered as a (1πu )1 electron
tronic terms, only shells and subshells with partially filled hole, the (1πu )3 (1π∗g )1 part of the configuration (82)
200 Fundamentals of Electronic Spectroscopy

y+ su* 2p su* 2p
2pz
y− pg* 2px , pg* 2py pg* 2px , pg* 2py
2p 2p 2p 2p
sg 2p
y− pu 2px , pu 2py

2px , 2py pu 2px , pu 2py

2s 2s sg 2p
su* 2s
y+
su* 2s
sg 2s 2s 2s
y−
sg 2s
2s
y+

su* 1s su* 1s
y− 1s 1s 1s 1s

1s sg 1s sg 1s
y+

(a) :+ :− (b) (c)

Figure 15 (a) Schematic representation of molecular orbitals in homonuclear diatomic molecules made from 1s, 2s, and 2p atomic
orbitals. Molecular-orbital energy diagram for homonuclear diatomic molecules formed from the lighter (b) and the heavier (c) atoms
from the second row of the periodic system of elements.

can be treated as the configuration 1(πu )1 (1π∗g )1 , which (1π∗g )1 ). Both the symmetric and the antisymmetric
leads to the terms + −
u , u and ∆u . Their energetic spatial parts are nonzero. Consequently, both singlet
order and multiplicities are derived in the next section. and triplet states are allowed, and configuration (81)
leads to the two terms 1 g and 3 g .
• Case 2
2.2.4 Spin Multiplicity
The two electrons are located in the same molecular-
As explained in Section 2.1.3, polyelectron wave functions orbital shell and in the same spatial orbital (φ 1 =
can be written as a product of a spatial part (Ψ R (qi )) and φ 2 ), so that Ψ R(a) (q1 , q2 ) = 0. The triplet state thus
a spin part (Ψ S (mi )): does not exist. This situation arises in the (1πg )2
configuration of O2 , when both electrons are located
Ψ (q1 , m1 , q2 , m2 , . . .) in either the λ = 1 or the λ = −1 orbital. In this
= Ψ R (q1 , q2 , . . .) × Ψ S (m1 , m2 , . . .) (85) case, Λ is equal to ±2 and the corresponding term
is 1 ∆g .
For simplicity, we consider here only two-electron wave • Case 3
functions and can therefore use the results presented The two electrons are located in the same molecular-
in Tables 4 and 5. The extension to more complicated orbital shell but in different orbitals. This situa-
situations is straightforward. Because a two-electron wave tion also arises in the (1πg )2 configuration of O2 ,
function must be antisymmetric under permutation of the when each of the two λ = ±1 orbitals is occu-
coordinates of the electrons, it must have either a symmetric pied by one electron (Λ = 0). The spatial part may
spatial part (Ψ R(s) (qi )) and an antisymmetric spin part be either symmetric (Ψ R(s) (q1 , q2 ) = (π+ (1)π− (2) +
√
(Ψ S(a) (mi )) or vice versa (Ψ R(a) (qi ) and Ψ S(s) (mi )). π+ (2)π− (1))/ 2), which results in a 1 g term,
In the determination of the multiplicity of an electronic or antisymmetric (Ψ R(a) (q1 , q2 )=(π+ (1)π− (2)−π+ (2)
√
term in accordance to Tables 4 and 5, three cases have to π− (1))/ 2), which corresponds to a 3 g term. To
be distinguished: determine whether these 1 g and 3 g terms are
− +
g or g , one has to determine their symme-
• Case 1 try with respect to the operation σv (see Table 8),
The two electrons are located in different molecular- which represents the reflection through an arbitrary
orbital shells, as in the configuration (81) ((3σg )1 plane containing the internuclear axis. Using the
 Fundamentals of Electronic Spectroscopy 201

form (76) for the π+ and π− functions, we establish the relative strength of the interactions that cou-
obtain ple the different electronic angular momenta. The treatment
is similar to that discussed for atoms in Section 2.1.4,
1 
Ψ R(a) (q1 , q2 ) = √ χ(z1 , ρ 1 )eiϕ 1 χ(z2 , ρ 2 )e−iϕ 2 with the important
 difference that only the projections
λi
2 (
Λ; Λ = i λi ) of the (total) orbital angular momentum

− χ(z2 , ρ 2 )eiϕ 2 χ(z1 , ρ 1 )e−iϕ 1 vectors
i (L) along the internuclear axis, rather than the
vectors
i and L themselves, are constants of motion in the
1
= √ χ(z1 , ρ 1 )χ(z2 , ρ 2 ) absence of spin–orbit coupling.
2 The strength of the spin–orbit coupling depends on
i(ϕ −ϕ )

× e 1 2 − e−i(ϕ 1 −ϕ 2 ) the molecule, the electronic configuration, and the inter-

√ nuclear separation. It is convenient to classify and label
= 2iχ(z1 , ρ 1 )χ (z2 , ρ 2 ) sin(ϕ 1 − ϕ 2 ) the electronic states according to idealized limiting cases,
(86) presented as cases (a)–(d) below, which form the start-
ing point of the widely used classification of angular
for the 3 term, and momentum coupling in rotating molecules originally intro-
√ duced by Hund (Hund 1926a,b, 1927a,b,c,d, 1928, 1930,
Ψ R(s) (q1 , q2 ) = 2χ (z1 , ρ 1 )χ(z2 , ρ 2 ) cos(ϕ 1 − ϕ 2 ) 1933) and extended by Mulliken (Mulliken 1930a,b,c,
1931, Mulliken and Christy 1931). If the rotational
(87)
motion is neglected, the relevant interactions are as
follows:
for the 1 term.
A σv reflection inverts the sign of (ϕ 1 − ϕ 2 ). Because 1. The interactions of the orbital motion of the electrons
of the relations sin(−x) = − sin(x) and cos(−x) = with the cylindrically symmetric electrostatic field of
cos(x), Ψ R(s) (q1 , q2 ) corresponds to the 1 +
g term and the nuclei. This interaction causes a precession of the
R 3 −
Ψ (a) (q1 , q2 ) to the g term. orbital angular momentum vectors around the internu-
Consequently, the (1πg )2 configuration of O2 pos- clear axis. Whereas neither
i nor L are constants of
sesses the three terms 3 − 1 +
g , g , and ∆g . The ener-
1 motion in cylindrical symmetry (compare Table 1 with
getically favorable exchange interaction in the triplet Tables 7 and 8), λi and Λ are good quantum numbers
term causes the X 3 − g state to be the ground state
in the absence of spin–orbit coupling. When the elec-
of O2 . trostatic interactions between electrons and nuclei are
strong, the terms resulting from the different config-
This procedure can be applied to arbitrary configu- urations are widely spaced in energy, and even the
rations. Table 10 summarizes the terms resulting from different terms of a given configuration are energeti-
the most common electronic configurations of diatomic cally well separated.
molecules. 2. The electrostatic exchange interaction: This interaction
The classification of terms presented in this section relies gives rise to an energetic splitting between states of
on the assumption that electrostatic (including exchange) different total electron-spin quantum number S, as
interactions are dominant and the effects of spin–orbit discussed in the previous section.
coupling can be disregarded. This assumption is justified 3. The spin–orbit interaction: The spin–orbit interaction
as long as the 2S+1 Λ terms are separated in energy by can be regarded as an interaction between the magnetic
an amount larger than the spin–orbit interaction. This moments resulting from the spin and orbital angular
tends to be the case in molecules made of light atoms, momentum vectors. This interaction can be described
for which spin–orbit interactions are genuinely weak, as inducing a precession of S (or si ) and L (or
i )
and at short internuclear distances, where the atomic around the resultant vectors J (or ji ) (see Section 2.1.4).
orbitals significantly overlap, the electronic motion is When the spin–orbit interaction becomes larger than
strongly coupled to the internuclear axis, and the exchange the exchange interaction, S ceases to be a good
interaction is substantial. Consideration of the spin–orbit quantum number.
interaction makes it necessary to extend the classification
of electronic terms. Angular Momentum Coupling Cases of the “LS-coupling”
type When interactions 1 and 2 above are larger than
interaction 3, situations analogous to LS coupling in atoms
2.2.5 Spin–Orbit Coupling
result that can be described by two limiting cases, called
To assess the effects of the spin–orbit coupling on the cases (a) and (b) that are discussed below. In both cases, S
electronic structure of diatomic molecules, one needs to and Λ are good quantum numbers.
202 Fundamentals of Electronic Spectroscopy

S excited state by ≈ 44 000 cm−1 . The two spin–orbit compo-

nents with Ω = 1/2, 3/2 are only separated by ≈ 120 cm−1 ,
“L”
and the ground state is X 2 1/2 . A weak coupling between
J
“L”
S
the vibrational and the electronic motion causes a depen-
dence of the spin–orbit constant (A in equation 88) on
hL hS hW the vibrational state (Av /(cm−1 ) = 123.26 − 0.1906(v +
1/2) − 0.018(v + 1/2)2 ) (Huber and Herzberg 1979).
(a) hW (b)
Case (b)
Figure 16 Electronic angular momentum coupling in the limit of In this second case, the spin–orbit interaction is neg-
(a) weak spin–orbit interaction (case (a)) and (b) strong spin–orbit ligible and S is not quantized along the internuclear axis.
interaction (case (c)). “L” is used instead of L to stress that L is Consequently, Σ is not defined and the 2S + 1 components
usually not a good quantum number in molecules. of the spin multiplet remain degenerate in the nonrotating
molecule. This case is characteristic of Λ = 0 states. The
Case (a) good electronic angular momentum quantum numbers in
In this first case, the electrostatic coupling of the orbital this case are Λ and S.
motion to the internuclear axis induces a fast precession
of L around the internuclear axis. On the longer timescale Example
of the weaker spin–orbit interaction, the precession of the
The [. . .][πu (2p)]4 [σg (2p)]1 X 2 +
g ground electronic state
orbital angular momentum vector is effectively averaged
of N2 + is separated from the first electronically excited state
out. L is perceived as a vector of length
Λ pointing along
by about 9000 cm−1 (Huber and Herzberg 1979). Except for
the internuclear axis, with magnetic moment −γ e Λ
. The
the twofold spin degeneracy, the situation is similar to that
orbital motion leads to a magnetic field pointing along the
in a 1 +
g state.
internuclear axis that then becomes the quantization axis
for the electron-spin vector S. S precesses with projection Angular Momentum Coupling Cases of the “jj -coupling”
quantum number Σ around the internuclear axis as a result Type When the spin–orbit interaction is stronger than
of the spin–orbit interaction (Figure 16a). Next to S, the the electrostatic interactions, S is not a constant of motion,
projection quantum numbers Λ and Σ and their sum Ω nor are the projections
Λ and
Σ of the orbital and
are good quantum numbers. Because of the spin–orbit spin angular momentum vectors. This situation can arise
coupling, the total energy depends on the relative sign of Σ either when the spin–orbit interaction is particularly large,
and Λ, so that usually only the absolute values of Λ and Ω for instance, in molecules containing heavy atoms (see
are used to designate the terms. The nomenclature 2S+1 ΛΩ case (c) below) or when the electrostatic coupling of the
is used, and the 2S + 1 components of the spin multiplet electronic angular momenta to the internuclear axis is
are split according to their spin–orbit interaction energies, particularly weak, for instance, in weakly bound molecules
which can be approximated by
or in Rydberg states (see case (d) below).

ESO = hcAΛΣ (88) Case (c)

In this case, the strong spin–orbit interaction couples the
where A (in cm−1 ) represents an effective spin–orbit cou- spin (si or S) and orbital (
i or L) angular momentum vec-
pling constant (compare with equation 37). The spin–orbit tors, which can be viewed as precessing around the resultant
splittings usually depend on the internuclear distance and vectors ( ji or Ja ). The weaker electrostatic coupling of the
thus on the vibrational level so that the spin–orbit coupling orbital motion to the internuclear axis leads to a slower
constant of a given vibrational level is further labeled with precession of the resultant vectors around the internuclear
the subscript “v” as Av . A and Av can be negative, in which axis with projection
Ω. The only good quantum number
case one speaks of inverted multiplets. Equation (88) can of the nonrotating molecule is Ω (see Figure 16b).
be regarded as a Paschen–Back effect induced by the elec-
trostatic field of the nuclei (see last term on the right-hand Example
side of equation 64).
The low-lying electronic states of Xe2 + (see Mulliken
(1970), and Zehnder and Merkt (2008)). Neglecting the
Example spin–orbit interaction, the electronic configurations A =
The [. . .][σ(2p)]2 [π(2p)]4 [π∗ (2p)]1 X 2 ground elec- [. . .][σg (5p)]2 [πu (5p)]4 [π∗g (5p)]4 [σu∗ (5p)]1 , B = [. . .]
tronic state of NO is separated from the first electronically [σg (5p)]2 [πu (5p)]4 [π∗g (5p)]3 [σu∗ (5p)]2 , C = [. . .][σg (5p)]2
 Fundamentals of Electronic Spectroscopy 203

II (1/2g)
A 2 Σ1/2u+ (sg)2 (pu)4 (pg)4 (su)1 D
II (1/2u)
su Xe+(2P1/2) + Xe(1S0)
C

Potential energy
B 2 ΠW g (sg)2 (pu)4 (pg)3 (su)2
pg I (1/2g)
I (3/2u) Xe+(2P ) + Xe(1S )
3/2 0
B
5p AO pu 5p AO I (3/2g)
2Π I (1/2u)
C Wu (sg )2 (pu )3 (pg )4 (su )2 A
sg Hund’s cases Hund’s case (c)
(a) + (b)
+
(a) D 2 Σ1/2g (sg)1 (pu)4 (pg)4 (su)2 (b) Internuclear distance

Figure 17 (a) Lowest four electronic configurations of Xe2 + in the notation introduced by Mulliken (1970). The bold arrows indicate
the electrons that are missing in the respective configurations. (b) Potential energy functions of the six corresponding low-lying electronic
states which can be described by cases (a) and (b) at short internuclear distances and by case (c) at large internuclear distances.

[πu (5p)]3 [π∗g (5p)]4 [σu∗ (5p)]2 , and D = [. . .][σg (5p)]1 Table 11 Spin–orbit interaction matrix describing the coupling
between the states of 2 + and 2 symmetry in the homonuclear
[πu (5p)]4 [π∗g (5p)]4 [σu∗ (5p)]2 give rise to four electronic rare-gas dimer ions.
states A 2 + 2 2 2 +
u , B g , C u , and D g (Figure 17a).
At short internuclear distances, the electrostatic interac- 2
+
1/2
2
1/2 2
3/2
tions lead to splittings that are larger than those resulting
2 +
from the spin–orbit interaction. Consequently, the two 2 + 1/2 V (R) − √a
2
0
and the two 2 states can be approximately described by 2
1/2 − √a2 V (R) + a
2 0
cases (b) and (a) presented above, respectively, and six 2
3/2 0 0 V (R) − a
2
states result: A 2 + 2 2 2
u , B 3/2g , B 1/2g , C 3/2u , C
2 2 +
1/2u , and D g (see left-hand side of Figure 17b). As
the internuclear distance increases, the electrostatic cou- Case (d)
pling to the internuclear axis weakens, and the spin–orbit This case arises when the electrostatic coupling of the
interaction starts dominating. As the internuclear distance electron orbital motion to the internuclear axis becomes
goes toward infinity, two dissociation limits result, the negligible. This case is encountered in Rydberg states
lower one being Xe 1 S0 + Xe+ 2 P3/2 and the upper one at large values of the principal quantum number of the
Xe 1 S0 + Xe+ 2 P1/2 . The energetic splitting between these Rydberg electron. In these states, the Rydberg electron
density in the region of the diatomic molecular ion core
two limits corresponds to the spin–orbit splitting of the
and, thus, the coupling of the electron to the internuclear
Xe+ ion (see right-hand side of Figure 17b). The lower
axis are very small, so that λ and Λ are not defined.
limit has Ja = 3/2, and thus four states, two Ω = 3/2
Usually, the Rydberg electron spin is not coupled to the
and two Ω = 1/2 states, designated by “I”, dissociate to
internuclear axis either, and the spin–orbit interaction of
this limit, whereas only two Ω = 1/2 states, designated
the Rydberg electron is negligible. A J + , j -type coupling
by “II”, dissociate to the upper limit which has Ja = 1/2. +
The Ω = 1/2 states of g (u) symmetry become equal mix- scheme [(2S +1) Λ+Ω+
]|n(sj ) similar to that described for
tures of the B 2 1/2g and D 2 + 2 + atoms by equation (46), and which represents the state as
g states (A u and C
2 a product of the electronic functions of the ion core and of
1/2u states) at large internuclear distances, and the Λ
the Rydberg electron, is adequate.
label becomes inadequate. The evolution from the coupling
cases (a) and (b) at short distances to case (c) at large
distances can be described semiquantitatively by consider- Example
ing the spin–orbit coupling matrix in Table 11 (Cohen and N2 : |[N2 + ] . . . (1πu )4 (1σg )1 2 +
g |20p.
Schneider 1974). The matrix, in the derivation of which
the spin–orbit coupling constant is assumed to be indepen-
2.2.6 Vibronic Structure
dent of the internuclear separation, clearly shows that the
spin–orbit interaction does not only split the 2 state into Diatomic molecules only possess one vibrational degree of
two components with Ω = 3/2 and 1/2 but also mixes the freedom, and thus one vibrational mode that corresponds
two Ω = 1/2 states. to a totally symmetric representation (1 +
g in D∞h and
204 Fundamentals of Electronic Spectroscopy

1
+ in C∞v ). The vibronic symmetry is thus the same perpendicular to the internuclear axis. The total angular
as the electronic symmetry. The energetic position of the momentum (without nuclear spins) J of a rotating molecule
vibrational energy levels relative to the minimum Teα of the is equal to
potential curve of the α th electronic state is given by
J=S+L+R=S+N (91)
 
1 1 2 where N represents the total angular momentum without
E v = Te + ω e v +
α α α
− ωe xe v +
α
2 2 electron spins. The quantum number R associated with
 3 R is only a good quantum number in molecules without
1
+ ωe yeα v + −··· (89) electronic angular momentum, i.e., in 1 states (J = N =
2
R), and this is why equation (90) can only be used for
where the second and subsequent terms are a consequence such states. In all other cases, the coupling between the
of the anharmonicity of the potential curve. spin, orbital, and rotational motions must be considered
explicitly. The spin–orbit and rotational motions can be
2.2.7 Rovibronic Structure described by the effective Hamiltonian
The treatment of the rotational structure of diatomic
molecules is sometimes reduced to the well-known formula: Ĥ = Ĥel + TN (Q) + ĤROT + ĤSO (92)

where the kinetic energy of the nuclei has been divided into
EROT = Bv J (J + 1) − Dv (J (J + 1))2 (90)
rotational motion ĤROT and vibrational motion TN (Q) as
explained in Merkt and Quack 2011: Molecular Quantum
which includes centrifugal distortion effects and also the
variation of the rotational and centrifugal distortion con- Mechanics and Molecular Spectra, Molecular Symme-
stants that results from the anharmonicity of the vibrational try, and Interaction of Matter with Radiation, this hand-
motion. Equation (90) is adequate to describe the rotational book. The spin–orbit coupling is described by
structure of states of 1 + symmetry, but it does not account
for the details of the rotational energy structure of states of ĤSO = AL̂ · Ŝ = A(L̂x Ŝx + L̂y Ŝy + L̂z Ŝz ) (93)
other electronic symmetry, for which the coupling of rota- which is adequate as long as the spin–orbit interaction
tional, orbital, and spin angular momenta must be consid- can be treated in an “LS”-like coupling manner, and the
ered. To present a complete treatment would extend beyond rotational motion by
the scope of this introductory article. We limit ourselves
here to qualitative considerations and a presentation of the 1 2
rotational structures of the simplest situations. The inter- ĤROT = 2
R̂ = B(r)[Ĵ − L̂ − Ŝ]2 (94)
2µR
ested readers are referred to the original articles of Hund
and Mulliken (Hund 1926a, 1927c,d, 1928, 1930, 1933, The classification in cases (a)–(d) made in Section 2.2.5
Mulliken 1930b,c, Mulliken and Christy 1931) and to the can be generalized to rotating molecules, as was first done
excellent overviews by Herzberg (1989), Hougen (1970), by Hund (1927c, 1930, 1933). The angular momentum
Zare (1988), Watson (1999b), Lefebvre-Brion and Field coupling schemes can be described by the vector models
(2004), and Brown and Carrington (2003) for more detailed depicted in Figure 18(a)–(d) (Zare 1988). The basis for
treatments. the classification is a hierarchical ordering of the interac-
Since diatomic molecules have a vanishing moment of tions similar to that introduced above for the nonrotating
inertia along the internuclear axis, the angular momen- molecules, but which now includes the interaction between
tum vector R describing the rotation of the nuclei lies the rotational and the electronic motion. The rotation of

S
S
L
J N
J
N J R J
R R
R
L S L
hΩ
hΛ
hΛ hΣ S Ja
hΩ
L
(a) (b) (c) (d)

Figure 18 Hund’s angular momentum coupling cases (a)–(d).

 Fundamentals of Electronic Spectroscopy 205

the molecule, with its inhomogeneous charge distribution, Hund’s Angular Momentum Coupling Case (c) In Hund’s
leads to a magnetic moment along R, which couples the case (c), the hierarchy of angular momentum coupling is
rotational motion to the electronic orbital and spin motions.
spin–orbit interaction
Hund’s Angular Momentum Coupling Case (a) This  coupling of L to internuclear axis
case arises when the energy splittings resulting from the
spin–orbit interaction (equation 88) are significantly larger  coupling of rotational and electronic motion (97)
than the separation ≈ 2BJ of two neighboring rotational
states. In this case, the hierarchy of interactions of the S and L couple to form an electronic angular momentum
angular momenta is as follows Ja , with component
Ω along the internuclear axis. J
represents the vectorial sum of R and
Ω (Figure 18c).
electrostatic coupling of L to internuclear axis The good quantum numbers in this case are Ω and J .

 spin–orbit coupling Hund’s Angular Momentum Coupling Case (d) In Hund’s

case (d), all angular momentum couplings are weak. Nei-
 coupling between rotational and electronic motion
ther L nor S is coupled to the internuclear axis. J is formed
(95) from (i) the vector addition of R and L to N and (ii) the
The total angular momentum J results from the vecto- vector addition of N and S to J. The good quantum numbers
rial addition of R and the components
Ω =
(Λ + ) are R, S, L, and J .
of the electronic angular momentum along the internu-
clear axis (Figure 18a). J, Ω, Λ, S and are good Example
quantum numbers in this case. The rotational motion
can be described as a rotation (nutation) of R and
Ω NO (1σ)2 (1σ∗ )2 (2σ)2 (2σ∗ )2 (3σ)2 (1π)4 (n p)1 Rydberg
around J. states. The electronic states can be represented by a closed-
The coupling between the rotational motion and the shell ground-state X 1 + NO+ cationic core surrounded
electronic motion increases with the degree of rotational by a weakly bound electron in a diffuse Rydberg orbital of
excitation. As J increases to large values, the coupling principal quantum number n and orbital angular momentum
of the electron spin (and ultimately also of the orbital) quantum number  = 1. Consequently, L = 1 and S = 1/2.
motion with the rotational motion becomes larger than the The rotational quantum number R is equal to that of the
spin–orbit coupling (and ultimately also larger than the ionic core. The weak interaction between L and R splits
electrostatic coupling of the orbital angular momentum to each rotational level into three levels with N = R, R ± 1,
the internuclear axis), so that this coupling case evolves which are each further split into doublets with J = N ± 1/2
first toward Hund’s case (b) and then toward Hund’s case by the still weaker interaction with the Rydberg electron
(d) as R increases and S and L get decoupled from the spin.
internuclear axis. These phenomena are referred to as S Angular Momentum Coupling Case (e) The treatment
and L uncoupling, respectively, and are described in more of Rydberg states with Λ > 0, S + > 0 open-shell ion cores
detail below. and of the rotational motion of weakly bound open-shell
molecules such as KrHe+ makes it necessary to introduce
Hund’s Angular Momentum Coupling Case (b) In Hund’s an additional angular momentum coupling case, case (e),
case (b), the spin–orbit coupling is negligible and S is not which exists in several variants as discussed in more detail
coupled to the orbital motion of the electrons. The hierarchy by Carrington et al. (1996), Watson (1999b), Brown and
of angular momentum coupling is Carrington (2003), and Lefebvre-Brion and Field (2004).
The situations described above as Hund’s cases (a)–(e)
coupling of L to internuclear axis represent idealized limiting cases. The sets of good quantum
 interaction between rotational and electronic motion numbers in these limiting cases are helpful in defining the
basis functions with which the Hamiltonian matrix describ-
 spin–orbit coupling (96) ing the rotational motion is most conveniently expressed.
Convenience can mean that one would like to have a Hamil-
The total angular momentum J results from (i) the vectorial tonian matrix that is as close as possible to a diagonal
addition of R with the component
Λ to form a total angular matrix, in which case one chooses the basis provided by
momentum without spin N and (ii) the addition of N and S the coupling case that describes the molecular system under
(Figure 18b). The good quantum numbers in Hund’s case study most closely. This approach has the advantage that
(b) are Λ, N, S, and J . the eigenvalues of the rotational matrix can be determined
206 Fundamentals of Electronic Spectroscopy

more easily, an advantage that was important in earlier

J Ω, Λ, SΣ|Jˆ2 |J Ω, Λ, SΣ =
2 J (J + 1) (102)
days, when computers were not available. Alternatively,
convenience can mean that one would like to set up the
J Ω, Λ, SΣ|Jˆz |J Ω, Λ, SΣ =
Ω (103)
Hamiltonian matrix using the basis providing the largest 

J Ω ∓ 1|Jˆ± |J Ω =
J (J + 1) − Ω(Ω ∓ 1) (104)
number of quantum numbers, i.e., the basis correspond-
ing to Hund’s case (a), regardless of which coupling case
J Ω, Λ, SΣ|Ŝ 2 |J Ω, Λ, SΣ =
2 S(S + 1) (105)
best describes the system under study. This procedure,
J Ω, Λ, SΣ|Ŝz |J Ω, Λ, SΣ =
Σ (106)
advocated by Hougen (1970), has the advantage that the 
treatment of the rotational structure can be made in a univer-
SΣ ± 1|Ŝ± |SΣ =
S(S + 1) − Σ(Σ ± 1) (107)
sal and straightforward manner. Although the Hamiltonian

J Ω, Λ, SΣ|L̂z |J Ω, Λ, SΣ =
Λ (108)
matrix may have more off-diagonal elements in this case,
the determination of the eigenvalues does not pose signifi-
Instead of setting up the Hamiltonian matrix (101) using
cant problems to present-day computers.
Hund’s case (a) basis functions |J Ω, Λ, SΣ, which do
The reasons why Hund’s angular momentum coupling
not have a well-defined parity, it is more convenient to use
cases still need to be introduced today are twofold: First,
as basis functions the linear combinations:
the hierarchy of interactions upon which the classification
is based is reflected by distinct spectral patterns. Second,
|J Ω, Λ, SΣ± = |J Ω, Λ, SΣ ± (−1)J −S+s
the electronic states are labeled by their good quantum
numbers, and the nomenclature thus depends on the Hund’s |J − Ω, −Λ, S − Σ (109)
coupling case that best describes them; for instance, the
ground electronic state of NO is labeled as X 2 3/2 , which have a well-defined parity (±). s in equation (109)
as appropriate for a system that can be approximately is 1 for Σ − states and 0 otherwise.
described by Hund’s case (a). The ground state of Xe2 + , on If the rotational and spin–orbit Hamiltonian matrix
the other hand, is labeled X 1/2u , or I(1/2u), as appropriate is expressed in Hund’s coupling case (a) basis set, the
for a system that can be approximately described by Hund’s first line of equation (101) only gives rise to diagonal
case (c). elements, with value AΛΣ + B(J (J + 1) + S(S + 1) −
In the treatment of the rotational structure of diatomic Λ2 − 2ΩΣ). The second line leads to off-diagonal ele-
molecules, ĤROT + ĤSO is set up in a matrix form using ments of the rotational matrix. Its effect is to mix states
standard relations of angular momentum algebra: with values of Σ and Ω differing by ±1, i.e., it mixes
different components of a spin–orbit multiplet. The mix-
Jˆ± = Jˆx ± iJˆy (98) ing becomes significant when the value of the off-diagonal
Jˆ+ Jˆ− + Jˆ− Jˆ+ element (≈ BJ ) becomes comparable to, or larger than, the
Jˆ2 = Jˆx2 + Jˆy2 + Jˆz2 = + Jˆz2 (99) energy separation (≈ A) between neighboring spin–orbit
2
components. This term thus decouples S from the inter-
Ĵ1 · Ĵ2 = Jˆ1x Jˆ2x + Jˆ1y Jˆ2y + Jˆ1z Jˆ2z nuclear axis (corresponding to the S uncoupling toward
Jˆ1+ Jˆ2− + Jˆ1− Jˆ2+ Hund’s case (b) mentioned above) and causes a splitting of
= + Jˆ1z Jˆ2z (100) the otherwise doubly degenerate rotational levels, with basis
2
functions |J Ω, Λ, SΣ±, of each spin–orbit component.
where Ĵ, Ĵ1 , and Ĵ2 represent arbitrary angular momentum The term in the third line of equation (101) couples
vectors and could also stand for Ŝ or L̂. Using these electronic states with Λ and Ω values differing by ±1, e.g.,
expressions, equation (94) can be rewritten as states with states. When such states are energetically
well separated, this term does not play a significant role,
ĤROT + ĤSO = ALz Sz + B(Jˆ2 + Ŝ 2 − L2z − 2Jz Sz ) but it can lead to noticeable perturbations of the rotational
structure if the separations between and states
− B(J+ S− + J− S+ ) − B(J+ L− + J− L+ )
 are accidentally small at certain J values. At very high
A values of J , this term starts to efficiently mix states of
+ + B (L+ S− + L− S+ )
2 different Λ values and to decouple L from the internuclear
 axis (corresponding to the L uncoupling toward case (d)
B
+ (L+ L− + L− L+ ) (101) mentioned above).
2
The term in the fourth line of equation (101) couples
The matrix elements arising from the different terms can states of the same Ω value but differing in their Λ and
be determined from standard results of angular momentum Σ values by ±1 and ∓1, respectively. In cases where
algebra, e.g., using the Hund’s case (a) basis |J Ω, Λ, SΣ the spin–orbit constant A becomes comparable or larger
 Fundamentals of Electronic Spectroscopy 207

than the spacing between, for instance, a 2 1/2 state and a Eq. (110)). Because |Λ| = |Ω| = 1, the lowest rotational
2
1/2 state, efficient mixing of these states results, but the level has J = 1. Perturbations caused by the term in the
other spin–orbit component of the state (2 3/2 ) remains third line of equation (101) may cause a J -dependent split-
unaffected. This situation has already been encountered in ting of the two components of each rotational level, an
the example of Xe2 + discussed in the previous section effect known as Λ doubling.
(Table 11) and leads to Hund’s case (c). 2
+ states:
The term in the fifth line of equation (101) does not
directly affect the rotational and spin–orbit structures but The rotational energy level structure of a 2 + state is
can shift the origin of a given electronic state. Western very similar to that of a 1 + state, with the difference that
(2011: Introduction to Modeling High-resolution Spec- each rotational level is now split into a doublet because
tra, this handbook) discusses the rotational energy level of the magnetic interaction between the rotational and
structure of several molecules. Here, we limit ourselves electron-spin motions. The energy level structure can be
to the treatment of the simplest cases of 1 + , 1 , 2 + , described phenomenologically by the following expressions
and 2 states. These examples can be generalized to more (the ± signs in the parentheses label the parity):
complex cases. However, when studying a specific case,
it is advisable to first consult the extensive literature on E(2 + , N, +) γN
= BN (N + 1) + (111)
diatomic molecules, in particular the textbooks by Herzberg (hc) 2
(1989), Lefebvre-Brion and Field (2004), and Brown and E(2 + , N, −) γ (N + 1)
Carrington (2003). The rotational energy level structures = BN (N + 1) − (112)
(hc) 2
(with symmetry labels) of the most commonly encoun-
tered electronic states of diatomic molecules are depicted where γ represents the spin-rotation coupling constant and
schematically in Figure 19. N the quantum number associated with the total angular
momentum excluding spin. This situation is characteristic
Example of Hund’s case (b).
1
+ states 2 states:
The rotational energy level structure of a diatomic The rotational energy level structure of a molecule in a
molecule in a 1 + state can be described to a good approx- 2
state can be obtained from the matrix ĤROT + ĤSO as
imation by equation (90). The parity of the rotational func- described above. Because both the total angular momentum
tions is determined in this case by the even/odd nature of quantum number J and the parity (p = ±) are good
the angular momentum quantum number J (J = R in a quantum numbers, the matrix has a block-diagonal form.
1 + state). Each block can be characterized by its parity and J value
and be represented by a (2 × 2) matrix:

2 2
3/2 , J, p √ 1/2 , J, p
2
3/2 , J, p B(J (J√+ 1) − 7/4) + A/2 −B J (J + 1) − 3/4 (113)
2
1/2 , J, p −B J (J + 1) − 3/4 B(J (J + 1) + 1/4) − A/2

1
states
Only the first, third, and fifth lines of equation (101)
The diagonal elements (AΛΣ + B(J (J + 1)) + S(S +
need be considered in this case, because S = 0. The term
1) − Λ2 − 2ΩΣ) correspond to the first line of equation
in the fifth line does not lead to any J dependence, and its
(101) and the off-diagonal elements to its second line. The
effects are incorporated into the purely electronic term
matrix (113) has the eigenvalues
value. The term in the third line can couple the 1 state with
neighboring 1 + and 1 − states. In the absence of such
E(2 , J, p)/(hc)
perturbations, the rotational levels of a 1 state are given by
 
1 3
E(1 , J, ±) =B J − J+
= B[J (J + 1) − 1] (110) 2 2
(hc) 

   2
1 3 A
and each rotational level is doubly degenerate and has ± J− J+ + − 1  (114)
one component of positive and one of negative parity (see 2 2 2B
208 Fundamentals of Electronic Spectroscopy

1 + − 2Σ + − 3Σ + −
Σ (g/u) / 1Σ (g/u) (g/u)
/ 2Σ (g/u) (g/u)
/ 3Σ (g/u) 1Π
(g/u) ∆(g/u)
1

+ − + − + −
Σ Σ Σ Σ Σ Σ
+ (s/a) − (a/s)
4 + / − (s/a) (a/s) 7/2, 9/2 4 +/ − (s/a) (a/s) 3–5 4 + /− (s/a) (a/s) 4 − (a/s)
4 + (s/a)

− (a/s) + (s/a)
3 − / + (a/s) (s/a) 5/2, 7/2 3 −/ + (a/s) (s/a) 2–4 3 − /+ (a/s) (s/a) 3 3
+ (s/a) − (a/s)

+ (s/a) − (a/s)
2 + / − (s/a) (a/s) 3/2, 5/2 2 +/ − (s/a) (a/s) 1–3 2 + /− (s/a) (a/s) 2 − (a/s)
2 + (s/a)

− (a/s)
1 − / + (a/s) (s/a) 1/2, 3/2 1 −/ + (a/s) (s/a) 0–2 1 − /+ (a/s) (s/a) 1 + (s/a)

0 + / − (s/a) (a/s) 1/2 0 +/ − (s/a) (a/s) 1 0 + /− (s/a) (a/s)

J=N J N J N J=N J=N
(a)

2Π 2Π 2∆
(g/u) (g/u) (g/u)

− (a/s) + (s/a)
5/2 5/2
+ (s/a) − (a/s)

+ (s/a) − (a/s)
7/2 7/2
− (a/s) + (s/a) + (s/a)
3/2
− (a/s)

− (a/s)
5/2, 7/2 − (a/s) N=3
+ (s/a)
+ (s/a)
5/2 − (a/s) + (s/a)
+ (s/a) 5/2
− (a/s)

+ (s/a) − (a/s)
3/2
− (a/s) J = 3/2 + (s/a)
+ (s/a)
+ (s/a)
3/2, 5/2 − (a/s) N=2
− (a/s) − (a/s)
J = 1/2 + (s/a)
2Π 2Π − (a/s)
− (a/s)
1/2 3/2 J = 1/2, 3/2 + (s/a) N=1 2
∆3/2 2∆
5/2
+ (s/a)

(b) Hund's case (a) Hund's case (b)

Figure 19 Rotational energy level structures of 1 + , 1 − , 2 + , 2 − , 3 + , 3 − , 1 , 1 ∆, 2 , and 2 ∆ states. The ± labels next to
the rotational levels indicate the parity of the rotational levels. The a/s label is only appropriate for homonuclear diatomic molecules
and designates the symmetry of the rovibronic wave functions with respect to permutation of the coordinates of the identical nuclei (see
Section 3.3.4 for more details). The g/u labels are also only relevant in homonuclear diatomic molecules and describe the symmetry of
the electronic function with respect to inversion through the center of symmetry.
 Fundamentals of Electronic Spectroscopy 209

The eigenfunctions have mixed 2 3/2 and 2 1/2 character, addition to the electron orbital and spin motions, the rota-
the mixing being caused by the off-diagonal elements which tional motion of the molecular framework must be consid-
are approximately equal to BJ . When BJ is much less ered in the treatment of the hyperfine structure of molecules.
than the energy difference (≈ A) between the diagonal A systematic classification of the possible angular momen-
elements, the mixing becomes negligible and the rotational tum coupling cases can be made following the same general
levels retain their 2 3/2 or 2 1/2 character. This situation principles as used in the discussion of Hund’s angular
corresponds to a pure Hund’s case (a). When BJ is much momentum coupling cases in the previous section. How-
larger than A, the splitting between the two levels is ever, the necessity to include the hyperfine interactions in
primarily given by the value of the off-diagonal elements, the hierarchical ordering of angular momentum couplings
and the Ω = 1/2 and 3/2 characters are fully mixed. This leads to an explosion of the number of limiting cases, par-
situation corresponds to Hund’s case (b). This example ticularly if Rydberg states are considered.
serves to show how the “S-uncoupling” term in the second The following nomenclature, introduced by Frosch and
line of equation (101) decouples S from the internuclear Foley (1952) (see also Dunn 1972), is used to label the
axis and recouples it to the rotational motion. It also limiting cases of the angular momentum coupling: The
shows that it is the relative magnitude of BJ and A letters (a)–(e) are used to describe the angular momentum
which determines whether the angular momentum coupling coupling scheme without nuclear spins. A right subscript
scheme is better described by Hund’s case (a) or (b). Each (α or β) is added to indicate whether the nuclear-spin
energy level described by equation (114) corresponds to motion is coupled to the internuclear axis or not. In the
two rotational states of opposite parity. former case (subscript α), the projection
Iz of the nuclear-
spin vector on the internuclear axis is well defined. In
Coupled 2 + and 2 states: When there is a strong the latter case (subscript β), the nuclear-spin vector is
mixing between neighboring 2 + and 2 states, induced by coupled to another angular momentum vector, i.e., R, N,
the term in the fourth line of equation (101), as in the case S, or J, which is added in the subscript next to β. For
of Xe2 + discussed in the previous section (see Table 11), a example, “aα ” implies a Hund’s case (a) coupling situation
Hund’s case (c) situation arises. In this case, the rotational (Figure 20a) in which the nuclear-spin I is coupled to the
energy levels can also be derived in a Hund’s case (c) internuclear axis. “bβS ” refers to a Hund’s case (b) coupling
formalism (Veseth 1973, Carrington et al. 1999): situation (Figure 20b) in which the nuclear spin is coupled
   to the electron-spin vector S, in which case the total spin
1 1 vector G = S + I results. “cβJ ” describes a Hund’s case (c)
E Ω = , J = T3/2 + B1/2 J (J + 1) −
2 2 situation (Figure 20f) in which the nuclear spin is coupled
 to J.
1 1
+ (−1)(J − 2 +q) P J + (115) In general, the hyperfine interactions are much weaker
2
   than the electrostatic (including exchange) and spin–orbit
3 9 interactions. Moreover, the Fermi-contact hyperfine inter-
E Ω = , J = T3/2 + B3/2 J (J + 1) − (116)
2 2 action, which is only of appreciable strength in electronic
states with a significant electron-spin density at the nuclei,
In equations (115) and (116), TΩ , BΩ , and P represent the is weak in Λ = 0 states because the nuclei are located in the
vibronic term energies, the rotational constants, and the Ω- nodal plane of the partially filled molecular orbitals. Con-
doubling constant, respectively. The phase factor (−1)q in sequently, “α-type” coupling cases, which can only arise
equation (115) (with q = 0 and 1 for electronic states of u as aα and cα cases, are rather unusual and more probable
and g symmetry, respectively), which is not present in the in Hund’s case (c) situations because the electronic wave
equation for heteronuclear diatomic molecules or molecules functions often contain significant contributions, even
with nuclei I = 0, was introduced in order to treat both when Ω = 0.
sets of states in 40 Ar2 + with the same formula (Rupper and Figure 20 illustrates schematically the vector models
Merkt 2002). corresponding to several of the angular momentum coupling
schemes mentioned above. The hyperfine structure of the
ground state (X 2 + + +
g (v = 0, N = 1)) of ortho H2
+
2.2.8 Hyperfine Structure +
and of para D2 depicted in figure 27 of Merkt et al.
As in the case of atoms, the hyperfine structure in molecules 2011: High-resolution Photoelectron Spectroscopy, this
results from the interaction of the magnetic-dipole and/or handbook, represents an example of case bβS .
electric-quadrupole moments of the nuclei having a nonzero An exhaustive discussion of the hyperfine structure of
nuclear spin I (|I|2 =
2 I (I + 1)) with the electric and diatomic molecules, which would go beyond the scope of
magnetic field distributions arising from other motions. In this introductory article, would need to include cases where
210 Fundamentals of Electronic Spectroscopy

aa a b(J ) bbs (for L = 0)

S
I
I
G
F J
R R F R F

L S I L S
hL hS hIz hL hS
(a) hF (b) (c)

bbJ (for L = 0) Ca Cb(J )

S
I
I
J
F J
R F
R F R

Ja I Ja

(d) (e) hW hIz (f) hW

Figure 20 Selected illustrative angular momentum coupling schemes in diatomic molecules, including nuclear spins: (a) case aα ; (b)
case aβ(J ) ; (c) case bβS ; (d) case bβJ ; (e) case cα ; and (f) case cβ(J ) . The nomenclature used to label these schemes is explained in the
text. More complex situations arise when two nuclear spins (I1 and I2 ) are considered or in the treatment of the hyperfine structure of
Rydberg states.

both nuclei have a (different) nuclear spin and would need 2.3.1 Molecular Orbitals, Electronic Configurations,
to describe the many coupling cases arising in Rydberg and Electronic States
states with their specific coupling cases (d) and (e). We
refer here to the “Further reading list” at the end of this Small Polyatomic Molecules with the Example of HAH
article for more extensive treatments. Molecules Molecules possessing the chemical formula
HAH (A designates an atom, e.g., Be, B, C, N, O, etc.)
are either linear and belong to the D∞h point group or bent
2.3 Polyatomic Molecules and belong to the C2v point group, the character table of
which is given in Table 12. Molecular orbitals are therefore
The electronic structure of polyatomic molecules can be classified either in the D∞h (see Table 8) or the C2v point
described using the same principles as those introduced group. For simplicity, we consider here only valence states
for diatomic molecules in the previous section. However, of HAH molecules with A being an atom from the second
the same polyatomic molecule can have different geome- or third row of the periodic table, so that  ≥ 2 atomic
tries and belong to different point groups depending on its orbitals can be ignored in the discussion of the electronic
electronic state. The variety of possible electronic states structure.
and molecular structures is so large that it is impossible
to give a complete overview in this article. We, there- Table 12 Character table of the C2v point group.
fore, restrict the discussion to only a few representative
molecular systems: molecules of the form HAH as proto- C2v I C2 σv (xz) σv
(yz)
typical small molecules, the cyclopentadienyl cation and
benzene as typical highly symmetrical molecules, and ade- A1 1 1 1 1 Tz α xx , α yy , α zz
A2 1 1 −1 −1 Rz α xy
nine as an example of a nonsymmetrical large molecule.
B1 1 −1 1 −1 Tx , Ry α xz
The principles that we describe are easily generalized to B2 1 −1 −1 1 Ty , Rx α yz
arbitrary molecules.
 Fundamentals of Electronic Spectroscopy 211

+ + + − z + + + − + −
2b2
sg su a1 b2 − +
2su − + − +
(a) (b)
+
4a1
Figure 21 Symmetry-adapted linear combinations of 1s orbitals − − 3sg − + −
Orbital
that participate in the construction of molecular orbitals of (a) −
energy
+
linear and (b) bent HAH molecules. + 1b1 1pu
−
−
+ −
The determination of the molecular orbitals may proceed + −
1b2
+

along the following scheme: −

3a1
+ + +
1su
1. Identification of all atomic orbitals participating in the 2a1 + + − −
+
formation of molecular orbitals. Symmetry restricts + + 2sg + + +
the number of these orbitals. In the case of HAH
molecules, the required orbitals are the two 1s orbitals 90°
∠HAH →
180°
z
of the hydrogen atoms and the ns and np valence
orbitals of the central atom A, where n ≥ 2 represents H
A
H
y H –A–H z

the row of the periodic system of elements to which A

belongs. Orbitals belonging to inner shells of the central
atom usually lie so deep in energy and are so strongly Figure 23 Walsh diagram for HAH molecules. The symmetry
labels on the left-hand side correspond to C2v point-group
localized on the nucleus that they hardly contribute to symmetry and those on the right-hand side to D∞h symmetry.
molecular bonds.
2. The formation of i symmetry-adapted molecular orb- nodal plane) orbitals in Figure 22 are bonding, whereas
itals from the set of i atomic orbitals determined under the 3σg (two nodal planes) and 2σu (three nodal planes)
(a) (i = 6 in the case of HAH molecules). Symmetry- orbitals are antibonding. For symmetry reasons, the 2px
adapted molecular orbitals transform as irreducible and 2py orbitals of the central atom (both of πu symmetry)
representations of the corresponding point group. In cannot combine with the 1s orbitals of the H atoms and are
molecules such as HAH in which two or more atoms therefore nonbonding orbitals.
are equivalent, it is convenient to first build symmetry- The energetic ordering of these molecular orbitals is
adapted linear combinations of the orbitals of these given on the right-hand side of Figure 23, which also
equivalent atoms, i.e., of the H 1s orbitals in the case shows how the energies of the molecular orbitals change
of HAH molecules (see Figure 21). These orbitals are as the molecule is progressively bent from the linear D∞h
then used to form molecular orbitals with the orbitals structure (∠(HAH) = 180◦ ) toward the C2v structure with
of the central atom A (or of other atoms in the case of ∠(HAH) = 90◦ . The orbitals of the bent molecules dis-
other molecules) having the corresponding symmetry, played on the left-hand side of Figure 23 are given symme-
as shown in Figure 22 for the point group D∞h . try labels of the C2v point group according to their trans-
The ns (σg ) and npz (σu ) orbitals of the central atom can formation properties (see Table 12). The two lowest-lying
be combined with the symmetry-adapted orbitals of the H orbitals are invariant under rotations around the C2 (z) axis,
atoms in two ways each, resulting in four molecular orbitals and also under reflection in both the σxz and σyz planes, and
of σ symmetry. The energetic ordering of these molecular are therefore totally symmetric (a1 ). The next higher-lying
orbitals can be derived from the number of nodal planes of orbital is antisymmetric under C2 rotation and under σxz
the wave functions. The 2σg (zero nodal plane) and 1σu (one reflection, but symmetric under σyz reflection, and is thus
of b2 symmetry. As in the linear geometry, the energetic
1s 2s 1s 1s 2pz 1s 1s 2s 1s 1s 2pz 1s
ordering essentially follows the number of nodal planes.
The degeneracy of the two nonbonding πu orbitals
is lifted as the molecule bends. The molecular orbital
+ + + + + − − − + − − + − +
2sg 1su 3sg 2su
corresponding to the p orbital in the molecular plane
becomes bonding and correlates with the 3a1 molecular
+ −
orbital of the bent molecule. The other molecular orbital,
− + which is perpendicular to the molecular plane, remains a
1pu
nonbonding orbital and correlates with the 1b1 orbital of
the bent molecule. The angle dependence of the 1πu − 3a1
Figure 22 Linear combinations of atomic orbitals in linear HAH orbital energy is of particular importance, because this
molecules. orbital is the only one that becomes significantly more
212 Fundamentals of Electronic Spectroscopy

stable in the nonlinear geometry. All other molecular level structure and gives rise to the Renner–Teller effect,
orbitals are destabilized when the HAH angle is decreased. which is discussed further in Section 2.3.6.
The occupation of this orbital with one or two electrons
Larger Symmetric Molecules To determine the molecu-
can result in a bent equilibrium structure of the molecule.
lar orbitals of larger polyatomic molecules that have a high
Correlation diagrams as the one shown in Figure 23 are
known as Walsh diagrams. symmetry, it is useful to introduce a systematic approach.
As in the case of atoms and diatomic molecules, the elec- The symmetrized linear combinations of atomic orbitals
tronic configurations of polyatomic molecules are obtained (LCAO) are determined using projection operators p̂γ that
by filling the molecular orbitals with a maximum of two are applied onto one of the atomic orbitals of the set of iden-
electrons. Whether a molecule of the form HAH is linear tical atoms. The projectors are defined as (see Merkt and
or bent depends on the occupation of the orbitals, espe- Quack 2011: Molecular Quantum Mechanics and Molec-
cially of the 3a1 orbital, as discussed above. The symmetries ular Spectra, Molecular Symmetry, and Interaction of
of the electronic states that result from a given config- Matter with Radiation, this handbook)
uration are obtained from the direct product of the irre- 1
γ
ducible representations of the occupied molecular orbitals p̂γ = χ (R)∗ · R̂ Projection formula (117)
h R
(see equation 84). Finally, the multiplicities (2S + 1) are
derived following exactly the same procedure as discussed where R̂ are the geometrical operations of the point group,
for atoms and diatomic molecules in the previous sections χ γ (R) is the character of the irreducible representation γ
(see also Section 2.3.2 below). under the operation R̂, and h is the order of the point group.
To illustrate the application of the projection formula
Examples (equation 117), we use it to derive the system of π
molecular orbitals of benzene in the D6h point group by
BeH2 : . . . (2σg )2 (1σu )2 building symmetry-adapted linear combinations
The dependence of the energies of the occupied orbitals
favors a linear structure (see Figure 23) and the ground

6

γ =
ϕ (s) cγ ,i ϕ i (118)
electronic state is therefore the X̃ 1 +
g state. i=1
BeH2 : . . . (2a1 )2 (1b2 )1 (3a1 )1 of the carbon 2pz orbitals ϕ i (i = 1 − 6). From the six 2pz
atomic orbitals involved in the π orbital system, which form
The first excited configuration leads to a bent structure
a six-dimensional reducible representation of the D6h point
because the 3a1 − 1πu orbital is occupied. The electronic
group, a total of six orthogonal molecular orbitals can be
configuration is thus given using C2v symmetry labels. The
formed. The reducible representation  of the carbon 2pz
two electronic states resulting from this configuration are
of 3 B2 and 1 B2 symmetry. orbitals can be constructed using the character table of the
D6h point group presented in Table 13.
H2 O: . . . (2a1 )2 (1b2 )2 (3a1 )2 (1b1 )2 Under the group operations of D6h , the 2pz orbitals ϕ i
Because the 3a1 orbital in H2 O is doubly occupied, the have the same symmetry properties as the components zi
electronic ground state is also bent. The ground electronic of the nuclear displacement vectors of the carbon atoms.
state is thus the X̃ 1 A1 state. The 2pz orbitals are mapped onto each other by the
+ 2
symmetry operations of the group. From the properties of
H2 O+ : . . . (2a1 )2 (1b2 )2 (3a1 )2 (1b1 )1 X̃ B1 . the representation matrices, it can be easily established that
H2 O+ also possesses a bent electronic ground state. • each orbital that is left unchanged by a symmetry
Walsh diagrams such as that displayed in Figure 23 are operation R̂ adds 1 to the character χ(R);
also useful in the discussion of vibronic interactions because • each orbital that is inverted adds −1 to the character;
they enable one to see how the degeneracy of π orbitals and and
of the , ∆, , . . . electronic states are lifted, and how the • each orbital that is mapped onto another orbital gives
electronic character changes, when the molecules bend out no contribution to the character.
of their linear structures. The coupling of electronic motion Thus, the characters of the reducible representation  of
and bending vibrations can significantly perturb the energy the six 2pz orbitals under the different classes of symmetry
operations R̂ are

c: E 2C6 2C3 C2 3C
2 3C

2 i 2S3 2S6 σh 3σd 3σv

χ(c): 6 0 0 0 −2 0 0 0 0 −6 0 2
 Fundamentals of Electronic Spectroscopy 213

Table 13 Character table of the D6h point group.

D6h E 2C6 2C3 C2 3C
2 3C

2 i 2S3 2S6 σh 3σd 3σv

A1g 1 1 1 1 1 1 1 1 1 1 1 1
A2g 1 1 1 1 −1 −1 1 1 1 1 −1 −1 Rz
B1g 1 −1 1 −1 1 −1 1 −1 1 −1 1 −1
B2g 1 −1 1 −1 −1 1 1 −1 1 −1 −1 1
E1g 2 1 −1 −2 0 0 2 1 −1 −2 0 0 Rx , Ry
E2g 2 −1 −1 2 0 0 2 −1 −1 2 0 0
A1u 1 1 1 1 1 1 −1 −1 −1 −1 −1 −1
A2u 1 1 1 1 −1 −1 −1 −1 −1 −1 1 1 z
B1u 1 −1 1 −1 1 −1 −1 1 −1 1 −1 1
B2u 1 −1 1 −1 −1 1 −1 1 −1 1 1 −1
E1u 2 1 −1 −2 0 0 −2 −1 1 2 0 0 x, y
E2u 2 −1 −1 2 0 0 −2 1 1 −2 0 0

This representation must now be transformed into a sum 3. e1g : For multidimensional subspaces, the projection
of irreducible representations using the reduction formula: technique usually yields nonorthogonal linear combi-
nations of the original basis vectors. To construct the
1
symmetry-adapted basis, it is sufficient to determine di
aγ = n(R)χ  (R)χ γ (R) (119)
h linearly independent vectors and then choose suitable
R
orthogonal linear combinations of them:
where aγ is the number of times the irreducible repre-
sentation γ is contained in the reducible representation , 1 1
h (= 24) is the order of the group, n(R) is the number of ϕ (s)
e1g ,1 = p̂e1g ϕ 1 = √ 2ϕ 1 + ϕ 2
N 12
operations of a particular class of operations, χ  (R) is the

character of the reducible representation corresponding to − ϕ 3 − 2ϕ 4 − ϕ 5 + ϕ 6 (123)

the class of the operation R̂, and χ γ (R) is the corresponding 1 1
character of the irreducible representation γ . ϕ (s)
e1g ,2 = p̂e1g ϕ 2 = √ ϕ 1 + 2ϕ 2
N 12
Reducing  using equation (119) yields the symmetries

of the six π molecular orbitals: + ϕ 3 − ϕ 4 − 2ϕ 5 − ϕ 6 (124)

 = b2g ⊕ a2u ⊕ e1g ⊕ e2u (120) The set of vectors {ϕ (s) (s)
e1g ,1 , ϕ e1g ,2 } is linearly indepen-
dent, but not orthogonal. A set of orthogonal basis
each of the two e irreducible representations being two
vectors can be obtained by using the Schmidt orthog-
dimensional. The orthonormal set of symmetry-adapted
onalization algorithm: if φ 1 and φ 2 are nonorthog-
basis functions {ϕ (s)
i } is constructed by projecting the ϕ i onal, normalized basis vectors, then a basis vector
on their irreducible components using equation (117) and
φ⊥
2 that is orthogonal to φ 1 can be constructed using
Table 13:
equation (125):
1. a2u :
  
φ⊥ 
1 1
2 = φ2 − φ2 φ1 φ1 (125)
a2u =
ϕ (s) p̂a2u ϕ 1 = √ ϕ 1 + ϕ 2 + ϕ 3 +ϕ 4 + ϕ 5 + ϕ 6
N 6
(121) where
.|. denotes the scalar product. Thus,
 (s)  (s)  (s)
ϕ (s),⊥ (s) 
e1g ,2 = ϕ e1g ,2 − ϕ e1g ,2 ϕ e1g ,1 ϕ e1g ,1
where N is a normalization constant. The normalization
factor √16 results from the assumption that the ϕ i
1 (s)
orbitals do not overlap. The same result is obtained = ϕ (s)
e1g ,2 − ϕ e1g ,1 (126)
by applying the projector to any other ϕ i , i = 1. 2
2. b2g :
After normalization, one obtains
1 1

ϕ (s)
b2g = p̂b2g ϕ 1 = √ ϕ 1 − ϕ 2 + ϕ 3 −ϕ 4 + ϕ 5 − ϕ 6 1

N ϕ (s),⊥
e1g ,2 = ϕ2 + ϕ3 − ϕ5 − ϕ6
6 (127)
(122) 2
214 Fundamentals of Electronic Spectroscopy

The set of symmetry-adapted basis vectors {ϕ (s) e1g ,a ,

nodal planes and has therefore the second lowest energy.
The e2u and b2g orbitals possess three and four nodal planes
ϕ (s)
e1g ,b } = {ϕ (s)
e1g ,1 , ϕ (s),⊥
e1g ,2 } for the e 1g subspace is thus
and are thus the orbitals of second highest and highest
energy, respectively.
1

e1g ,a = √
ϕ (s) 2ϕ 1 + ϕ 2 − ϕ 3 − 2ϕ 4 − ϕ 5 + ϕ 6 A more quantitative estimate of the relative energies of
12 the molecular orbitals can be achieved using the Hückel
(128) molecular-orbital (HMO) model. The HMO model repre-
1
sents a simple semiempirical method to calculate the elec-
ϕ (s)
e1g ,b = ϕ + ϕ3 − ϕ5 − ϕ6 (129) tronic energy level structure of molecules that exhibit con-
2 2
jugated π molecular orbitals such as polyenes and aromatic
4. e2u : Similarly, one obtains an orthonormal set of molecules. The model is useful to gain a semiquantitative
symmetry-adapted basis vectors for the e2u sub- description of the π molecular orbitals and their relative
space: energies and is widely used in physical–organic chemistry.
Within the framework of the HMO model, the π molecular
1

e2u ,a = √
ϕ (s) 2ϕ 1 − ϕ 2 − ϕ 3 + 2ϕ 4 − ϕ 5 − ϕ 6 orbitals are constructed by linear combinations of orthogo-
12 nal 2pz atomic orbitals centered on the carbon atoms. The
(130) energies Ek of the π molecular orbitals are obtained by
1
solving the secular determinant
ϕ (s)
e2u ,b = ϕ2 − ϕ3 + ϕ5 − ϕ6 (131)
2  
detHij − Ek Sij  = 0 (132)
These molecular orbitals are depicted in Figure 24. Their
energetic ordering can be determined from the number where Hij are the matrix elements of a formal Hamiltonian
of nodal planes. The a2u orbital must be the most stable operator H describing the π electron system (the “Hückel
because it possesses a single nodal plane (the plane operator”) and Sij denotes the overlap integral between the
containing the carbon atoms). The e1g orbital possesses two pz orbitals of atoms i and j . The expansion coefficients
ci(k) of the molecular orbital k in the basis of the atomic
E 2pz orbitals {ϕ i } are obtained by solving the set of secular
equations:
b2g a – 2b

ci(k) Hij − Ek Sij = 0 (133)

i

The following approximations are introduced:

e2u a–b

• All overlap integrals vanish (Sij = 0) unless i = j , in

which case Sii = 1.
• All diagonal elements of H are the same: Hii = α.
e1g a+b • All off-diagonal elements of H are set to zero, except
those between neighboring atoms, which are Hij = β.
β is usually negative (β < 0).

a2u a + 2b α and β are treated as effective parameters that can in

principle be estimated from calorimetric data.
The matrix representation of the Hückel operator H
describing the π molecular-orbital system can be derived
Figure 24 Energy level diagram and schematic representation
of the π molecular orbitals of benzene. The size of the circles in the basis of the carbon 2pz atomic orbitals {ϕ i }, and is
represents the weight of the atomic orbital in the molecular-orbital  
wave function. The two gray tones of the shading indicate the α β 0 0 0 β
relative sign of the 2pz orbitals that form the molecular orbital. β α β 0 0 0
 
The energies of the molecular orbitals increase with the number   0 β α β 0 0
Hij = 
0
 (134)
of nodal planes and are expressed, on the right-hand side of the
 0 β α β 0
figure, as a function of the Hückel parameters α and β. The arrows 0
represent schematically the occupation of the molecular orbitals 0 0 β α β
in the ground-state configuration of benzene. β 0 0 0 β α
 Fundamentals of Electronic Spectroscopy 215

The eigenvectors and eigenvalues of the matrix (134) repre- case, in two 1 × 1 diagonal blocks corresponding to A2u
sent the molecular orbitals and their energies, respectively. and B2g and two 2 × 2 diagonal blocks corresponding to
Alternatively, the Hückel operator can be expressed in the E1g and E2u . The fact that the Hamiltonian matrix is fully
basis of symmetry-adapted basis functions {ϕ (s)
i } by evalu-
diagonal in equation (137) is a consequence of the par-
ating the matrix elements according to ticular choice made during the Schmidt orthogonalization
procedure.
   (s) 
Hij(s) = ϕ (s)   The lowest energy configuration of π electrons in ben-
i H ϕj (135)
zene can thus be written (a2u )2 (e1g )4 , giving rise to a single
using the basis functions given in equations (121, 122, 128, electronic state of symmetry 1 A1g . The first excited elec-
129–131). For the ϕ (s)
a2u orbital (equation 121), one finds, for tronic configuration of benzene is (a2u )2 (e1g )3 (e2u )1 . This
instance, configuration gives rise to several electronic states, as dis-
cussed in Section 2.3.2. The direct product of the partially
   (s)  1    occupied orbitals is e1g ⊗e2u = b1u ⊕ b2u ⊕ e1u . Since two
  ϕ 1 + ϕ 2 + ϕ 3 + ϕ 4 + ϕ 5 + ϕ 6 Hϕ 1
a2u H ϕ a2u =
ϕ (s)
different spatial orbitals are partially occupied, there is no
6
 restriction on the total electron spin imposed by the general-
+ ϕ2 + ϕ3 + ϕ4 + ϕ5 + ϕ6
ized Pauli principle (Section 2.2.4), and all electronic states
= α + 2β (136) contained in the direct product can exist as either singlet or
triplet states. The configuration (a2u )2 (e1g )3 (e2u )1 thus gives
Matrix elements between functions of different symmetry rise to the electronic states 3 B1u , 1 B1u , 3 B2u , 1 B2u , 3 E1u ,
and matrix elements between orthogonal basis functions and 1 E1u .
within the e1g and e2u subspaces are zero because H is To illustrate the case where each orbital of a degenerate
totally symmetric, so that one obtains the following Hückel pair of orbitals is singly occupied, we now present the
matrix: group-theoretical and HMO treatments of the electronic
structure of the cyclopentadienyl cation C5 H5 + using the
 (s) 
Hij D5h point group, the character table of which is presented
  in Table 14.
α + 2β 0 0 0 0 0 The matrix representation of the Hückel operator can be
 0 α − 2β 0 0 0 0 
  determined in analogy to benzene and takes the following
 0 0 α+β 0 0 0 
= 0
 form:
 0 0 α+β 0 0   
 0 0 0 0 α−β 0  α β 0 0 β
 
0 0 0 0 0 α−β   β α β 0 0 
Hij =   0 β α β 0 
 (138)
(137) 0 0 β α β
which is already in diagonal form. The symmetry-adapted β 0 0 β α
orthonormal basis functions {ϕ (s)
i } are thus the eigenvec-
tors of the Hückel operator and represent the π molec- Diagonalization of this matrix gives rise to the five eigen-
ular orbitals {i } of benzene depicted in Figure 24. One values α + 2β, α + ω2 β (twice), and α + ω1 β (twice),
should note that a group-theoretical treatment normally only where ω1 and ω2 are defined in Table 14. The applica-
divides the Hamiltonian matrix in as many diagonal blocks tion of the reduction formula (equation 119) to the five-
as there are irreducible representations, i.e., in the present dimensional reducible representation of the five pz orbitals

Table 14 Character table of the D5h point group.

D5h E 2C5 2C25 5C2 σh 2S5 2S25 5σd

A
1 1 1 1 1 1 1 1 1
A
2 1 1 1 −1 1 1 1 −1 Rz
E
1 2 ω2 ω1 0 2 ω2 ω1 0 x, y
E
2 2 ω1 ω2 0 2 ω1 ω2 0
A

1 1 1 1 1 −1 −1 −1 −1
A

2 1 1 1 −1 −1 −1 −1 1 z
E

1 2 ω2 ω1 0 −2 −ω2 −ω1 0 Rx , Ry
E

2 2 ω1 ω2 0 −2 −ω1 −ω2 0

ω1 = 2 cos(4π/5) and ω2 = 2 cos(2π/5).

216 Fundamentals of Electronic Spectroscopy

E J23 − K23 , 2h + J23 + K23 , and 2h + J22 + K23 , respec-

C5H5+ 1A ′ tively, where h, Jij , and Kij represent the one-electron
1
e2″ orbital energy, the Coulomb integral, and the exchange
2K 23 integral, respectively, and the indices designate the π
molecular orbitals in order of increasing energy (Borden
1E ′
2 1982; by symmetry, J22 − J23 = 2K23 ). Using the HMO
e1″ approach, one can determine the one-electron energy to be
2K 23
h = α + ω2 β.
a2″ 3A ′
2

(a) (b) Large Polyatomic Molecules Unlike small polyatomic

molecules, most large molecules have a low symmetry, and
Figure 25 (a) Frost–Musulin diagram of the π molecular the classification of electronic states by their irreducible
orbitals of the cyclopentadienyl cation. The arrows indicate the representations loses its relevance. When the molecule
occupation corresponding to the lowest lying electronic configura-
tion. (b) Energetic ordering of the corresponding electronic states possesses no symmetry elements, all electronic transitions
in D5h symmetry (right-hand side). K23 represents the exchange involving nominally a single electron are allowed by
integral. [See text; adapted from Wörner and Merkt (2007).] symmetry. Consequently, a different nomenclature is used
to label both the electronic states and the electronic
transitions of large molecules, as already mentioned in the
and of the projection operators gives rise to five eigenvec- introduction.
tors of symmetries a

2 , e

1 , and e

2 . The energetic ordering of The electronic states are designated by a capital letter
the corresponding orbitals is depicted in Figure 25(a) in the representing their spin multiplicity: S for singlets, D for
form of a Frost–Musulin diagram. A Frost–Musulin dia- doublets, T for triplets, etc. A numerical subscript is used
gram is derived by drawing a regular polygon representing to indicate the ground state (e.g. S0 ) and the higher lying
the cyclic polyene into a circle, placing one vertex on the excited states of the same multiplicity (S1 , S2 , etc.). States
lowest point of the circle. The vertices of the polygon then of another multiplicity of the same molecule are also
provide the energies of the π orbitals of the polyene. Such labeled in order of increasing energies but starting with
diagrams provide an elegant graphical method to deter- the subscript “1” rather than “0” (e.g., T1 , T2 , etc.).
mine the sequence and degeneracy of the HMO of cyclic Electronic transitions in polyatomic molecules are often
polyenes. Looking at Figure 24, it becomes apparent that labeled according to the type of molecular orbitals involved.
a Frost–Musulin diagram indeed adequately describes the One distinguishes between bonding orbitals of σ or π type,
HMOs of benzene. the corresponding antibonding orbitals (σ∗ or π∗ ) and non-
The most stable electronic configuration of C5 H5 + is bonding orbitals (n). This nomenclature has the advantage
((a

2 )2 (e

1 )2 ), as depicted in Figure 25(a). The direct product that it highlights the nature of the electronic transition,
of the irreducible representations of the partially occupied from which qualitative predictions of their intensities can
orbitals is e

1 ⊗ e

1 = a
2 ⊕ e
2 ⊕ a
1 . In this case, the two be made: transitions involving the excitation of an electron
components of a degenerate orbital may both be singly from a bonding to the corresponding antibonding orbital
occupied. The total electronic wave function must be anti- (σ → σ∗ or π → π∗ ) are usually associated with a large
symmetric under the exchange of the two electrons in the oscillator strength, whereas transitions from nonbonding to
e

1 orbitals, which restricts the number of possible states, antibonding orbitals (n → σ∗ or n → π∗ ) are weak.
as is discussed in general terms in Section 2.3.2. The elec- The nomenclature outlined above is often used in the
tronic symmetry of the singlet states, which have an anti- discussion of the photochemistry and photophysics of
symmetric (with respect to permutation of the electrons) larger molecules, such as the DNA bases. Although the
electron-spin function, must be determined from the sym- isolated DNA bases absorb strongly in the ultraviolet
metric (rather than 

the

direct) product of the irreducible (200–300 nm), they hardly show any fragmentation, unlike
representations e1 ⊗ e1 = e2 ⊕ a
1 , resulting in a 1 E
2 and


many other molecules. This property may be of importance
a 1 A
1 state. Correspondingly, the electronic symmetry of in preserving the genetic information (Sobolewski and
the triplet state is obtained from the antisymmetric prod- Domcke 2002) and arises from the ability of the molecules
uct {e

1 ⊗ e

1 } = a
2 , resulting in a single 3 A
2 state (compare to convert the energy of the photon to vibrational energy,
with the analogous discussion of the electronic structure as is discussed in Section 3.5.3.
of O2 in Section 2.2.4). The energetic ordering of the Adenine also represents a good example, illustrating the
three states 3 A
2 , 1 E
2 and 1 A
1 is given in Figure 25(b). difficulty associated with all nomenclature systems for large
The Hartree–Fock energies of these three states are 2h + molecules. The sequence of singlet states consists of the S0
 Fundamentals of Electronic Spectroscopy 217

0 400 800 1200 cm−1 E

NH2 D E
N 1ππ*
Log signal (arb. unit)
N
H
H N N 1n π*
H

35 430 39 930
×2
B C

S0
35 430 35 830 36 230 36 630 37 030
Wave number (cm−1)

Figure 26 Resonance-enhanced two-photon ionization spectrum of adenine in the gas phase. The bands A and D are assigned to the
origins of the n → π∗ and π → π∗ excitations, respectively. The bands B, C, and E are vibronic levels of mixed electronic character.
The right-hand side of the figure shows an energy level diagram of the three lowest electronic singlet states of adenine. [Reproduced
from Kim et al. (2000).  American Institute of Physics, 2000.]

ground state with the configuration . . . (π)2 (n)2 (π∗ )0 , fol- quantum number (λ in the case of diatomic molecules).
lowed by two electronic states of dominant configurations, However, group theory provides a simple approach to
. . . (π)2 (n)1 (π∗ )1 and . . . (π)1 (n)2 (π∗ )1 , respectively. determining the existing multiplicities. Two cases can be
One can only indicate the dominant configurations for these distinguished:
two electronic states because they lie energetically very
close, and configuration interaction between them is impor- 1. The two electrons are located in different molecular-
tant. Since the energetic ordering of these states has been orbital shells. Both the symmetric and the antisymmet-
debated in the literature (see Sobolewski and Domcke 2002 ric spatial parts of the wave functions are nonzero in
and references therein), it is difficult to apply the usual this case. No restrictions result from the Pauli princi-
labels S1 and S2 to these electronic states. To avoid this dif- ple: the electronic states are given by the direct product
ficulty, the recent literature uses the designation 1 nπ∗ and of the representations of the partially occupied orbitals,
1 ππ∗ for these two states, the 1 superscript designating the and all terms contained in the direct product exist as
spin multiplicity. Figure 26 shows a resonant two-photon both singlet and triplet states. This situation arises in
ionization spectrum of adenine in a supersonic expansion the first excited states of BeH2 arising from the configu-
and a diagram of the electronic energy levels as derived ration . . . (2a1 )2 (1b2 )1 (3a1 )1 discussed in the first part
from this spectrum (Kim et al. 2000). The band labeled of Section 2.3.1. Since b2 ⊗ a1 = b2 , the two electronic
“A” was assigned to the origin of the 1 nπ∗ state, whereas states 3 B2 and 1 B2 are obtained. The same applies
band “D” was assigned to the origin of the 1 ππ∗ state. to the (a2u )2 (e1g )3 (e2u )1 configuration of benzene dis-
The wave-number scale on top of Figure 26 is given with cussed in the section Larger Symmetric Molecules in
respect to band “A”. The energy-integrated absorption of the Section 2.3.1, giving rise to the electronic states
the 1 ππ∗ state is strong, and the band turns into a broad 3
B1u , 1 B1u , 3 B2u , 1 B2u , 3 E1u , and 1 E1u .
absorption band above 36 230 cm−1 . 2. The two electrons are located in the same molecular-
orbital shell. If the molecular-orbital shell is nonde-
2.3.2 Spin Multiplicity generate, the spatial part of the wave function is nec-
essarily symmetric. The spin part must therefore be
As in the treatment of diatomic molecules in section 2.2.4, antisymmetric, resulting in a totally symmetric (A
1 for
we will only consider two-electron wave functions. Because benzene) singlet state. If the molecular-orbital shell is
of the Pauli principle, the two-electron wave function must degenerate, the spatial part has both symmetric and
either have a symmetric spatial part (Ψ R(s) (qi )) and an antisymmetric components. The symmetry properties
antisymmetric spin part (Ψ S(a) (mi )) or vice versa (Ψ R(a) (qi )) of these components are determined by the symmet-
and (Ψ S(a) (mi )); see Tables 4 and 5. ric and antisymmetric parts, respectively, of the direct
The situation is slightly different from the case of product of the orbital symmetry with itself. This situa-
diatomic molecules, because the components of degenerate tion arises in the (a

2 )2 (e

1 )2 configuration of C5 H5 + as
orbitals can no longer be classified according to a good discussed in the section Larger Symmetric Molecules
218 Fundamentals of Electronic Spectroscopy

Table 15 Character table of the spin double group C22v . The description of spin–orbit coupling in polyatomic
molecules requires the use of the spin double groups. Such
C2v I C2 σv (xz) σv
(yz) R groups are obtained from the corresponding point groups
A1 1 1 1 1 1 Tz by including 2π rotations with negative character to take
A2 1 1 −1 −1 1 Rz into account the fact that a half-integer spin function has
a periodicity of 4π. The character table of the spin double
B1 1 −1 1 −1 1 Tx , Ry
group for C2v and C3v molecules are presented in Tables 15
B2 1 −1 −1 1 1 Ty , Rx
and 16, respectively, and Table 17 shows how the spin
E1/2 2 0 0 0 −2 functions with S = 0, 1/2, 1, 3/2, . . . transform in these
spin double groups.
The first five rows and columns correspond to the C2v point group
(Table 12). We first consider the case where spin–orbit coupling is
small compared to the rotational intervals of the molecule.
Spin–orbit interaction splits a rotational state of total angu-
Table 16 Character table of the spin double group C23v . lar momentum (without spin) N into (2S+1) nearly degen-
erate states. As an example, we consider a C2v molecule in
C3v I 2C3 σv R 2C23
its 2 B1 electronic ground state. The ground rovibronic state
A1 1 1 1 1 1 Tz has the symmetry rve = B1 . The spin-rovibronic symme-
A2 1 1 −1 1 1 Rz tries of this level are thus srve = rve ⊗ S=1/2 = B1 ⊗
E 2 −1 0 2 −1 Tx,y , Rx,y E1/2 = E1/2 , showing that the spin-rovibronic ground state
E1/2 2 1 0 −2 −1 is doubly degenerate. The same holds true for all other rovi-
E3/2 2 −2 0 −2 2 bronic levels of this electronic state. However, the degener-
acy may be lifted in the rovibronic levels of a C2v molecule
The first four rows and columns correspond to the C3v point group. in a 3 B1 electronic state. In this case, the rovibronic
ground state gives rise to spin-rovibronic levels of symme-
tries srve = rve ⊗ S=1 = B1 ⊗ (A2 + B1 + B2 ) = B2 ⊕
in the Section 2.3.1. The symmetric 

spatial part of
A1 ⊕ A2 .
the wave function is given by e1 ⊗ e1 = e
2 ⊕ a
1 ,


A more interesting case occurs in molecules of the C3v
resulting in a 1 E
2 and a 1 A
1 state. Correspondingly, the
point group, such as, e.g., the methyl halides CH3 X (X =
triplet state is obtained from the antisymmetric product
halogen atom) and their cations. The cations CH3 X+ have
{e

1 ⊗ e

1 } = a
2 , resulting in a single 3 A
2 state.
. . .(e)3 2 E ground electronic states. Neglecting vibronic
interactions (see Section 2.3.6), spin–orbit coupling splits
2.3.3 Spin–Orbit Coupling their ground electronic state into two components of
symmetry E ⊗ E1/2 = E1/2 ⊕ E3/2 . In CH3 I+ , these two
Spin–orbit coupling in polyatomic molecules can lead to components are separated by ≈ 0.5 eV, corresponding to
very complex spectral patterns and dynamical behaviors a case where spin–orbit coupling gives rise to much larger
(e.g., intersystem crossings; see Section 3.5.3). To keep splittings than the vibronic interactions. We note that, in this
the discussion simple, we only treat here the limiting case, the effects of vibronic interactions (the JT effect) are
cases where the spin–orbit coupling is small compared strongly suppressed (see also Köppel et al. 2011: Theory
to the energy intervals between neighboring rotational of the Jahn–Teller Effect, this handbook for details).
energy levels, and the opposite case where the spin–orbit We now illustrate the transition between the limit-
coupling is very large, even larger than the splitting between ing cases of weak and strong spin–orbit coupling with
electronic states of different multiplicities caused by the the example of the (X̃ 2 E)(ns) Rydberg states of CH3 X
exchange interaction. The first case is related to Hund’s (X = halogen), which have the electronic configura-
case (b) and the second case to Hund’s case (c) describing tion . . . (e)3 (a1 )1 . In low Rydberg states, the exchange
the angular momentum coupling in diatomic molecules interaction between the Rydberg electron and the ionic
(Section 2.2.5). core is larger than the spin–orbit coupling, resulting in

Table 17 Transformation properties of the spin functions in the spin double groups C2v and C3v .

S 0 1/2 1 3/2 2 5/2

 (C2v ) A1 E1/2 A2 + B 1 + B 2 2E1/2 2A1 + A2 + B1 + B2 3E1/2

 (C3v ) A1 E1/2 A2 + E E1/2 + E3/2 A1 + 2E 2E1/2 + E3/2
 Fundamentals of Electronic Spectroscopy 219

Small Large explained in Merkt and Quack (2011): Molecular Quan-

spin–orbit spin – orbit (Ion) tum Mechanics and Molecular Spectra, Molecular Sym-
coupling coupling
metry, and Interaction of Matter with Radiation, this
1
E E handbook. The vibronic symmetry of a vibrationally excited
E1/2
molecule can be determined from the direct product:

ev = e ⊗ vn11 ⊗ vn22 ⊗ . . . (139)

A1
A2
3
E E where the product extends over all normal vibrations, and
E3/2
E ni is the number of vibrational quanta in the individual
vibrational modes.
Figure 27 Energy levels of an electronic state of configuration
. . . (e)3 (a1 )1 of a C3v molecule for small and large spin–orbit Example
coupling constants. On the right-hand side the lower two E
states correlate with the E3/2 electronic state resulting from the H2 O has three vibrational modes, two of A1 symmetry (the
. . . (e)3 configuration of the ion, whereas the upper group of symmetric stretching mode (ν 1 ) and the bending mode (ν 2 ))
states correlates with the E1/2 ionic electronic state of the same and one of B2 symmetry (the asymmetric stretching mode
configuration. [Adapted from Herzberg (1991).]
(ν 3 )). The vibronic symmetry of the (0, 0, 1) vibrational
state of the electronic ground state of H2 O is therefore
A1 ⊗ B2 = B2 .
a 3 E state and a 1 E state, as illustrated in Figure 27.
Spin–orbit coupling splits the 3 E state into E⊗ (E ⊕ A2 ) = Degenerate vibrational modes create a vibrational angular
A1 ⊕A2 ⊕E⊕E states. The 1 E state remains unaffected in the momentum that can couple with the electronic angular
weak-coupling limit. In high Rydberg states, the spin–orbit momentum.
interaction in the CH3 X+ ion is much larger than the
exchange interaction between the Rydberg electron and the Example
core electrons, and the level structure displayed on the right- CO2 + in its ground electronic state (X 2 ig ) is a lin-
hand side of Figure 27 is obtained. In that limit, the spin ear molecule with four vibrational modes: the symmetric
of the ion core is coupled to its orbital angular momen- stretching mode, the twofold-degenerate bending mode, and
tum, giving rise to the E3/2 and E1/2 levels discussed in the the asymmetric stretching mode. Single excitation of the
previous paragraph. The Rydberg electron is only coupled bending mode (v = u ) results in a vibrational angu-
weakly to the ion core by the exchange interaction, which lar momentum
l with l = 1 along the C∞ axis. The
scales as n−3 . The symmetries of the electronic states can interaction of this vibrational angular momentum with the
thus be obtained by taking the direct product of the symme- electronic angular momentum (the Renner–Teller effect,
try of the ionic state and the Rydberg electron. Each Ryd- see also Köppel et al. 2011: Theory of the Jahn–Teller
berg level of the ns series converging to the 2 E3/2 ground Effect, this handbook and Section 2.3.6) leads, according
state gives rise to two E levels (E3/2 ⊗ E1/2 = E ⊕ E), to equation (139) and Table 9, to four vibronic states of
whereas levels converging to the 2 E1/2 state split into symmetries 2 + 2 − 2
u , u , ∆3/2u , and ∆5/2u .
2
three levels (E1/2 ⊗ E1/2 = A1 ⊕ A2 ⊕ E). Figure 27 bears
a close resemblance to Figure 3, representing the transition
from LS to jj coupling in atoms. 2.3.5 Rovibronic Structure and Symmetry
The rotational structure of polyatomic molecules is dis-
2.3.4 Vibronic Structure and Symmetry cussed in detail in Bauder 2011: Fundamentals of Rota-
tional Spectroscopy, this handbook.
The vibrational structure of polyatomic molecules is dis- Since the interactions between rotational, spin, and
cussed in detail in Albert et al. 2011: Fundamentals of orbital motions can often be neglected in polyatomic
Rotation–Vibration Spectra, this handbook, and so only molecules, their rotational structure can be treated in simple
a very brief description of the vibronic structure of poly- terms as eigenstates of a purely rotational Hamiltonian (see
atomic molecules is presented here. Bauder 2011: Fundamentals of Rotational Spectroscopy,
Linear and nonlinear polyatomic molecules have 3N − 5 this handbook). If the electron spins play a role, the
and 3N − 6 vibrational degrees of freedom, respectively. rovibronic states split into multiplets that can be classified
The transformation properties of the vibrational modes in the appropriate spin double group, as explained in
can be determined in a normal coordinate analysis, as Sections 2.3.2 and 2.3.3.
220 Fundamentals of Electronic Spectroscopy

2.3.6 Vibronic Coupling: The Renner–Teller and angular momentum 
about the axis as shown in
Jahn–Teller Effects Figure 28. The two angular momenta couple to form a total
vibronic angular momentum ±
K with K = | ± Λ ± |.
The Born–Oppenheimer approximation (see Section 1
As an example, we consider C3 , with point group D∞h
and also Merkt and Quack 2011: Molecular Quantum
in the linear configuration, in its à 1 u first excited singlet
Mechanics and Molecular Spectra, Molecular Symme-
electronic state. If only the bending vibrational mode is
try, and Interaction of Matter with Radiation and Bauder
excited with a single quantum (vbend = 1), |Λ| = || = 1,
2011: Fundamentals of Rotational Spectroscopy, this
which leads to four vibronic levels with K = 2, 2, 0, 0. The
handbook) allows the separation of nuclear and electronic
symmetry of the resulting vibronic levels is easily predicted
degrees of freedom, provided that the separation between
from group theory: ev = u (e) ⊗ u (v) = + −
g + g +
the electronic states is significantly larger than the vibra-
∆g . The two states have K = 0 and the ∆ state possesses
tional intervals. In many polyatomic molecules, partic-
two components with K = 2. The energetic ordering of
ularly in excited electronic states, this condition is not
these vibronic states is as shown in Figure 28.
fulfilled, which results in a coupling of electronic and
In general, a vibrational level with vbend quanta of exci-
nuclear motions called vibronic coupling. Vibronic coupling
tation has a vibrational angular momentum quantum num-
is ubiquitous in electronically excited states, especially in
ber  = −vbend , −vbend + 2, . . . , +vbend − 2, +vbend . The
the vicinity of intersecting potential energy surfaces (con-
vibronic levels of a state thus have the vibronic quan-
ical intersections) where it is essential in understanding
tum numbers K = −vbend − 1, −vbend + 1, . . . , +vbend −
photochemical and photophysical processes. Special cases
1, +vbend + 1 with the following vibronic symmetries: K =
characterized by a high molecular symmetry, such as the
0 : ; |K| = 1 : ; |K| = 2 : ∆; . . ..
“Renner–Teller” and “Jahn–Teller (JT) effects” are par-
The Renner–Teller effect has a strong influence on the
ticularly interesting because they enable one to study the
potential energy surfaces. The degeneracy of the two com-
vibronic interactions in detail, thanks to symmetry selection
ponents of a electronic state in the linear configuration is
rules. Comprehensive theories of vibronic coupling have
lifted when the molecule bends, resulting in two potential
been formulated (see Köppel et al. 2011: Theory of the
energy surfaces V + and V − . For symmetry reasons, the
Jahn–Teller Effect, this handbook; Bersuker 2006). Here,
functional form of the potential energy surface of a elec-
we provide a brief overview of the Renner–Teller and JT
tronic state in the absence of a Renner–Teller effect can
effects and refer to Theory of the Jahn–Teller Effect, this
only contain even powers of the bending coordinate Q:
handbook for details.
The Renner–Teller effect occurs in degenerate elec-
V 0 = aQ2 + bQ4 + · · · (140)
tronic states ( , ∆, , . . .) of linear molecules. These
states are characterized by an electronic angular momentum
For the same symmetry reasons, the splitting between the
±Λ
along the internuclear axis as shown in Figure 28.
V + and V − surfaces can also only contain even powers
Vibrationally excited bending levels possess a vibrational
of Q
E
V + − V − = αQ2 + βQ4 + · · · (141)
Gev =
In general, three qualitatively different types of potential
→ energy functions along the bending coordinate can be
L L = +1 Σ+
obtained, as illustrated in Figure 29. In the first case (a),
u bend = 1
∆ the RT effect is so weak that it preserves the linearity
→
= −1 of the molecule and only affects the curvature of the
Σ− potential energy surface along the bending mode. In the
second case (b), the lower-lying surface has a minimum at
a bent geometry, whereas the higher-lying surface retains
Figure 28 Electronic and vibrational angular momenta in the its minimum at the linear geometry. Finally, in the last
Renner–Teller effect of a linear triatomic molecule in a 1 case (c), both surfaces have their minimum shifted to a
electronic state, with its bending mode being excited with a single bent geometry. In cases (b) and (c), the molecules are
quantum. The left-hand side of the figure illustrates the case of permanently distorted only if the depth of the potential
electronic (vibrational) angular momentum projection quantum well significantly exceeds the zero-point energy of the
number Λ = +1 ( = −1). The right-hand side shows the splitting
of the vbend = 1 level into three sublevels of vibronic symmetries bending vibration. If the potential energy minimum occurs
− and + (Λ +  = 0), and ∆ (|Λ − | = 2) arising from the at a nonlinear geometry but the well depth is comparable
Renner–Teller effect. to or smaller than the zero-point energy of the bending
 Fundamentals of Electronic Spectroscopy 221

∞
 
V +V −
1
∂ k V̂
3N−6

V V V V̂ (Q) = k
Qki + V (Q0 ) (142)
k! ∂Qi
k=1 i=1 0

where Qi represents the vibrational coordinates. In many

V+ cases, the expansion can be truncated at k = 1 or 2, corre-
sponding to linear and quadratic JT activity, respectively.
V+
V− Group theory can be used to predict which modes are JT
“active”. The general selection rule for vibronic coupling
Qbend Qbend Qbend between two electronic states of irreducible representations
V−
(a) (b) (c) A and B mediated by a vibrational mode of symmetry
ν is
Figure 29 Adiabatic potential energy surfaces resulting from a
Renner–Teller effect in a degenerate electronic state of a linear
A ⊗ B ⊇ [ν ]k (143)
molecule induced by the bending mode.

where [ν ]k is the symmetric k-th power of the irreducible

representation of the vibrational mode ν. When equation
vibration, the molecule essentially behaves like a linear (143) is fulfilled, the vibrational mode is said to be an active
molecule. This is a special case of the so-called quasilinear mode of order k. According to equation (143), vibronic
molecules; however, quasilinearity can also be encountered coupling of order k between the different components of
in the absence of the Renner–Teller effect. a degenerate electronic state of irreducible representation
A classical example of the Renner–Teller effect repre- el, deg. , which is the simplest case of the JT effect, is
sented in Figure 29(c) is the à 2 A1 ← X̃ 2 B1 transition of allowed along mode ν if
NH2 . The potential energy minima in the X̃ and à states  2
occur at very different bending angles (103.4◦ and 144◦ , el, deg. ⊇ [ν ]k (144)
respectively), resulting in a long progression of the bend-
ing vibration in the electronic spectrum (Johns et al. 1976). Vibronic coupling between a degenerate state (el, deg. ) and
Examples for cases (a) and (b) are the à 1 u state of C3 a nondegenerate state (el, nondeg. ), the so-called pseudo-JT
effect, can only occur along mode ν if
and the X̃ 2 A1 and à 2 u states of BH2 , respectively.
The JT effect describes the geometrical distortion of
el, deg. ⊗ el, nondeg. ⊇ [ν ]k (145)
nonlinear molecules in degenerate electronic states (Jahn
and Teller 1937) of symmetries E, F, G, and H. Historically, To illustrate the JT and pseudo-JT effects, we now
threefold degenerate states were designated with the letter consider the examples of the cyclopentadienyl radical
T instead of the letter F. Both nomenclatures are in use in (C5 H5 ) and cation (C5 H5 + ), which are subject to a JT
the literature. As stated by Jahn and Teller, “any nonlinear effect and a pseudo-JT effect in their ground doublet and
molecular system in a degenerate electronic state will be lowest singlet states, respectively (see also Section 2.3.1 for
unstable and will undergo distortion to form a system of a treatment of the molecular orbital structure of C5 H5 + ).
lower symmetry and lower energy thereby removing the In their most symmetric configuration, C5 H5 and C5 H5 +
degeneracy”. The theorem of Jahn and Teller does not have D5h symmetry (see character table in Table 14). Rel-
state how large the distortion should be or which of the evant for a discussion of the low-lying electronic states
distortions allowed by symmetry will be the dominant one. of C5 H5 is the π-system of molecular orbitals already
As in the case of the Renner–Teller effect, the driving presented in the section Larger Symmetric Molecules in
force for the molecular distortion is the stabilization of Section 2.3.1. C5 H5 has the ground electronic configu-
the electronic structure that is achieved in the distorted ration ((a

2 )2 (e

1 )3 ), which gives rise to a single elec-
configuration. tronic ground state of 2 E

1 symmetry. In the D5h point
 2
The JT effect profoundly modifies the potential energy group, E

1 = A
1 ⊕ E
2 (see Table 18), so that the vibra-
surfaces. They are usually described in Taylor expansions tional modes of e
2 symmetry mediate a linear JT cou-
 2  2
around a reference geometry Q0 , most conveniently chosen pling. Since e
1 and e

1 both contain e
2 , vibrational
as the geometry of highest symmetry. At this geometry, modes of symmetry e
1 and e

1 are quadratically JT active
the electronic state has its maximal degeneracy (Bersuker (see equation 144). In D5h (M), linear and quadratic JT
2006, Domcke et al. 2004, Köppel et al. 1984, Barckholtz activities are therefore mutually exclusive, which leads to
and Miller 1998, Wörner and Merkt 2009) cylindrically symmetric potential energy surfaces in the
222 Fundamentals of Electronic Spectroscopy

Table 18 Irreducible representations  of D5h and their sym- according to equation (145), and is discussed here using
metrized squares []2 . the cyclopentadienyl cation as an example. The three low-
est electronic states of the cyclopentadienyl cation result
 a
1 a
2 e
1 e
2 a

1 a

2 e

1 e

2
[]2 a
1 a
1 a
1 + e
2 a
1 + e
1 a
1 a
1 a
1 + e
2 a
1 + e
1
from the configuration ((a

2 )2 (e

1 )2 ) and have the electronic
symmetries 3 A
2 , 1 E
2 , and 1 A
1 (in order of increasing
energy; see Section 2.3.1). These electronic states have
been investigated by photoelectron spectroscopy (Wörner
E
et al. 2006, Wörner and Merkt 2007, 2009). The triplet
ground state is not involved in vibronic coupling and there-
fore has a D5h equilibrium geometry. The doubly degener-
ate 1 E
2 state undergoes both JT and pseudo-JT effects. From
equation (144) and Table 18, one can conclude that the e
1
vibrational modes are linearly JT active, and that the e
2
and e

2 vibrational modes are quadratically active in the 1 E
2
state. However, the JT effect in an electronic state having
VE(0) two electrons in two degenerate orbitals (configuration e2 )
vanishes in the absence of configuration interaction (Wat-
son 1999a) and will therefore be neglected. The pseudo-JT
VE(0) – Estab q y coupling between the 1 E
2 and 1 A
1 states (e
2 ⊗ a
1 = e
2 ) is
x r mediated by vibrational modes of e
2 symmetry in first order
and modes of e
1 or e

1 symmetry in second order. The poten-
Figure 30 Adiabatic potential energy surfaces resulting from a
tial energy surfaces of the second and third lowest electronic
linear Jahn–Teller effect in a doubly degenerate electronic state
induced by a single doubly degenerate vibrational mode with states of C5 H5 + are represented schematically in Figure 31.
coordinates x and y. For a single doubly degenerate PJT-active mode with Carte-
sian coordinates (x, y) or cylindrical coordinates (r, φ), two
respective two-dimensional subspaces of degenerate vibra- of the surfaces repel each other whereas the third remains
tional coordinates. The ground-state potential energy sur- unchanged. Assuming identical vibrational frequencies in
face of C5 H5 is schematically represented in Figure 30.
A vibrational mode of symmetry E can be represented V
using two Cartesian coordinates (x, y) or two cylindrical
coordinates (ρ, θ ) related by

x = ρ cos(θ ) and y = ρ sin(θ ) (146)

In the case of a single linearly JT-active mode of symmetry

E, the potential energy surface of a doubly degenerate
electronic state takes the following form:
ωJT 2
VE± (ρ, θ ) = VE± (ρ) = VE (0) + ρ ± gρ (147)
2
where VE (0) is the electronic potential energy at the
reference geometry, ωJT is the frequency of the vibrational
mode, and g is the JT coupling constant. The corresponding
shape of the potential energy surfaces is illustrated in
Figure 30. The linear JT effect thus decreases the potential
energy of the lower component of the E electronic state by y
the stabilization energy: j

x r
g2
Estab = (148)
2ωJT Figure 31 Adiabatic potential energy surfaces resulting from a
linear Pseudo-JT effect between a lower-lying doubly degenerate
The pseudo-JT effect occurs when a vibrational mode electronic state (E) and a higher-lying nondegenerate state (A)
couples a degenerate and a nondegenerate electronic state, induced by a single doubly degenerate vibrational mode.
 Fundamentals of Electronic Spectroscopy 223

the A and E states, the following potential surfaces are For the case of linearly polarized radiation with electric-
obtained: field vector, E = (0, 0, E) and, therefore, V̂ = −M̂Z E.
VE (0) + VA (0) ωPJT 2 When studying the spectra of atoms, the laboratory-fixed
VA (r, φ) = VA (r) = + r (or space-fixed) reference frame is the only relevant frame,
2 2
 because it can always be chosen to coincide with an
 
VA (0) − VE (0) 2 internal, “atom-fixed” reference frame. Indeed, the pointlike
+ + 2λ2 r 2 nature of the nucleus implies that there are no rotations of
2
the nuclear framework. For this reason, atomic spectra are
ωPJT 2
VEy (r, φ) = VEy (r) = VE (0) + r simpler to treat than molecular spectra.
2 In molecules, the components µ̂ξ of the electric-dipole
VE (0) + VA (0) ωPJT 2 moment have a simple expression, and can be computed
VEx (r, φ) = VEx (r) = + r
2 2 or interpreted easily in the molecule-fixed reference frame

  (x, y, z) in which they are given by (Fig. 41 of Merkt and
VA (0) − VE (0) 2
− + 2λ2 r 2 Quack 2011: Molecular Quantum Mechanics and Molec-
2 ular Spectra, Molecular Symmetry, and Interaction of
(149) Matter with Radiation, this handbook)
where VE (0) and VA (0) are the electronic potential energies

at the reference geometry, ωPJT is the frequency of the µ̂ξ = qj ξ j with ξ = x, y, or z (152)
vibrational mode, and λ is the pseudo-JT coupling constant. j
The corresponding shape of the potential energy surfaces is where qj and ξ j are the charge and the ξ coordinate of the
illustrated in Figure 31. j -th particle, respectively, and the sum extends over all par-
The spectroscopic characterization of the JT and pseudo- ticles (electrons and nuclei) in the molecule. The important
JT effects in C5 H5 and C5 H5 + is discussed in Section 3.4.3. quantities for the interaction defined in equation (151) are
the space-fixed components M̂X , M̂Y and M̂Z of M̂. To
3 ELECTRONIC SPECTRA evaluate equation (150) using equations (151) and (152),
one must express the space-fixed components of M̂ as a
3.1 Transition Moments and Selection Rules function of the molecule-fixed components µ̂ξ using three
angles, the Euler angles (θ , φ and χ). The Z component,
The intensity I (ν fi ) of a transition between an initial state for instance, is given by
of an atom or a molecule with wave function Ψ i and energy


Ei and a final state with wave function Ψ f and energy MˆZ = λxZ µ̂x + λyZ µ̂y + λzZ µ̂z = λαZ µ̂α (153)
Ef is proportional to the square of the matrix element V̂fi , α
where the matrix V̂ represents the operator describing the (see Eq. (318) of Merkt and Quack 2011: Molecular
interaction between the radiation field and the atom or the Quantum Mechanics and Molecular Spectra, Molecular
molecule: Symmetry, and Interaction of Matter with Radiation,
this handbook and their Figure 42) where the values of the
I (ν) ∝ |
Ψ f |V̂ |Ψ i |2 =
f|V̂ |i2 = V̂if2 (150)
direction cosines λiJ are given, e.g. in Zare (1988).
The transition is observed at the frequency ν fi = |Ef − The selection rules can be derived from the integral
Ei |/ h.
A selection rule enables one to predict whether a
Ψ f |M̂z |Ψ i  (154)
transition can be observed or not on the basis of symmetry
arguments. If
Ψ f |V̂ |Ψ i  = 0, the transition f ← i is said We begin the discussion of electronic transitions and selec-
to be “forbidden” , i.e., not observable; if
Ψ f |V̂ |Ψ i  = 0, tion rules by considering wave functions of the form
the transition f ← i is said to be “allowed”. given by equation (1). The product form of such func-
The interaction between molecules and electromagnetic tions is based on the assumption that the electronic, spin,
radiation of a wavelength much larger than the molec- vibrational, and rotational motions are separable, which
ular size is dominated by the interaction between the represents an approximation. The interactions between
electric-dipole moment and the electric field of the radiation the various types of motion, e.g., spin–orbit interaction
(Section 2.1.4) or the interaction between rotational and
V̂ = −M̂ · E (151) electronic motions (Section 2.2.7), or interactions between
vibrational and electronic motion (Section 2.3.6) are often
and, in the following, we restrict the discussion to this significant, in which case the selection rules derived on the
interaction. basis of equation (1) may be violated.
224 Fundamentals of Electronic Spectroscopy

In the following we proceed along the same lines as in momentum. The electric-dipole-moment operator M̂ is a
the more general discussion of selection rules in Merkt vector and can therefore be represented as a spherical tensor
and Quack 2011: Molecular Quantum Mechanics and of rank J = 1 (Zare 1988, Bauder 2011: Fundamentals of
Molecular Spectra, Molecular Symmetry, and Inter- Rotational Spectroscopy, this handbook). Consequently,
action of Matter with Radiation, this handbook. Using the transition moment
Ψ
|M̂ |Ψ

 vanishes unless
equations (1) and (153), equation (154) can be written as
!   ∆J = J
− J

= 0, ±1 (0 ↔ 0 forbidden) (160)







 
elec espin vib rot nspin  λαZ µ̂α 
 α  Considering the polarization of the radiation leads to the
" following selection rules for the magnetic quantum number:


elec 

espin 

vib 

rot 

nspin (155)
∆MJ = MJ
− MJ

= 0
The electric-dipole-moment operator (equation 152) is (linear polarization parallel to Z axis) (161)
independent of the spin variables. The integration over elec-
∆MJ = MJ
− MJ

= ±1
tron and nuclear-spin coordinates in equation (155) may
thus be performed separately from the integration over spa- (linear polarization perpendicular to Z axis) (162)
tial (rovibronic) coordinates
∆MJ = MJ
− MJ

= 1
# $# $

espin |

espin 
nspin |

nspin (circular polarization with positive helicity) (163)
!   "

 ∆MJ = MJ
− MJ

= −1
 

elec 
vib 
rot  λ µ̂  





(156)
 α αZ α  elec vib rot (circular polarization with negative helicity) (164)
The wave functions corresponding to different electron- The electric-dipole-moment operator is also antisymmetric
spin and nuclear-spin states are orthogonal, so that the first with respect to the parity operation, which reverses the sign
two integrals in equation (156) are zero, unless |
espin  = of all coordinates in the laboratory-fixed frame. Given that
|

espin  and |
nspin  = |

nspin . The resulting selection the parity is a conserved quantity as long as parity violation
rules imply the conservation of the total electron spin by the weak force is neglected (see Quack 2011: Fun-
damental Symmetries and Symmetry Violations from
∆S = 0 (157) High-resolution Spectroscopy, this handbook), transitions
can only occur between rovibronic states of opposite par-
and the total nuclear spin
ity, i.e.,
∆I = 0 (158)
+↔− (+ ↔ + and − ↔ − are forbidden) (165)
and also the conservation of nuclear-spin symmetry.
It is important to note that the ± signs in equation (165)
In the absence of interactions between the vibronic and
refer to the total (rovibronic) parity of the energy levels
rotational degrees of freedom, the vibronic wave functions
(equation 109) and must be distinguished from the ± signs
elec vib are independent of the Euler angles and so are
in the electronic term symbol. The parity selection rule is
the molecule-fixed components µ̂α of the electric-dipole-
discussed in more detail in Section 3.3.4 in the treatment
moment operator. Morover, the direction cosine matrix
of the rotational structure of electronic transitions.
elements λαZ and the rotational functions rot do not
Equations (160)–(165) are general to all electric-dipole
depend on the vibronic coordinates. Consequently, the
transitions in all systems, not only atoms. When the transi-
integration over the vibronic coordinates and the Euler
tions connect hyperfine levels, J

(and J
) must be replaced
angles in the last factor of equation (156) can be performed
by F

(and F
), respectively. Equations (157) and (158)
separately to a good approximation:
are also general to all electric-dipole transitions but hold
!   "

 less strictly because they result from the approximation of



 






elec vib rot  λ µ̂     separable wave functions.
 α αZ α  elec vib rot These considerations make it obvious that two-photon

     transitions (e.g., Raman transitions) or magnetic-dipole
= 
rot |λαZ | 

rot 
elec 
vib µ̂α  

elec 

vib (159)
transitions do not obey the same set of selection rules. The
α
treatment of such transitions can be made in an analogous
The first, angle-dependent factor on the right-hand side manner, but by using the appropriate form of the interaction
of equation (159) implies the conservation of angular operators.
 Fundamentals of Electronic Spectroscopy 225

Further selection rules, specific of the symmetry proper- of the nuclear framework, and the integration over the elec-
ties of the atomic or molecular systems under investigation, tronic coordinates in equation (167) can be performed for
result from the second, angle-independent term on the right- any given value of the nuclear coordinates Q
hand side of equation (159). These selection rules can be
derived from group-theoretical arguments on the basis of

vib [

elec |µ̂α |

elec e ]

vib  =

vib |µeα (Q)|

vib  (169)
the following considerations:
In equation (169),
1. electronic elec and vibrational vib wave functions
transform as irreducible representations of the appro- µeα (Q) =

elec |µ̂α |

elec e (170)
priate point group;
2. the molecule-fixed components µ̂ξ of the electric- depends on the nuclear coordinates Q and thus on the 3N −
dipole-moment operator transform as the translations 6 (or 3N − 5 for linear molecules) symmetrized normal
Tx , Ty , and Tz ; coordinates Qi . When this dependence is weak, µeα (Q) can
3. a product of two or more functions transforms as the be expanded in a Taylor series around a reference geometry,
product of the corresponding representations; and e.g., the equilibrium geometry Qeq of the initial electronic
4. the integral over a product of functions differs from state of the transition,
zero only if the product of the corresponding represen-
∂µe
tations contains the totally symmetric representation, µeα (Q) = µeα (Qeq ) + α
|eq Qj + . . . (171)
∂Qj
usually A1 (or + in diatomic molecules and S in j
atoms; we use A1 in this section to designate this
where the summation extends over all normal coordinates
representation).
Qj . Retaining only the constant and linear terms of the
An allowed transition between the states i and f with the Taylor series of µeα (Q), equation (169) can be expressed as
irreducible representations i and f must, therefore, fulfill a sum of two terms:
the condition in the electric-dipole approximation:
∂µe
µeα |eq

vib |

vib  + α
|eq

vib |Qj |

vib  (172)
∂Qj
i ⊗ (Tα ) ⊗ f ⊇ A1 with α = x, y, z (166) j

Equation (172) forms the basis of the classification of

Considering the last, vibronic, factor in equation (159), electronic transitions as electronically allowed transitions,
on the one hand, and as electronically forbidden, but


elec 
vib |µ̂α |

elec 

vib  =

ev |µ̂α |

ev  (167) vibronically allowed transitions, on the other hand. These
two types of electronic transitions are now described in
one concludes that a transition is vibronically allowed if more detail.

Electronically Allowed Transitions In the case of an

ev ⊗ (Tα ) ⊗ ev ⊇ A1 (168)
electronically allowed transition, the contribution arising




from the first term of equation (172) is nonzero, which
where ev and ev represent the vibronic symmetries of the implies that
initial and final state, respectively.




elec ⊗ (Tα ) ⊗ elec ⊇ A1 with α = x, y, z (173)
Example
Neglecting the second term in equation (172) leads to
In the C2v point group, Tx , Ty , and Tz transform as
the following two conclusions. First, the intensity of an
B1 , B2 and A1 , respectively (Table 12). Vibronic wave

electronically allowed transition is proportional to the
functions of symmetry ev = B1 , B2 , or A1 can thus be


= A square of the electronic transition moment evaluated at
excited from an initial vibronic state of symmetry ev 1 the equilibrium geometry of the initial state, i.e., to
(e.g., the ground state of H2 O), and the corresponding |

elec |µ̂α (Qeq )|

elec |2 . Second, the intensity of a transi-
transition moment lies along the x, y, and z axes of the tion from the vibrational level 

vib of the initial state to the
molecule-fixed reference frame, respectively. Transitions vibrational level 
vib of the final state is proportional to the


to levels of vibronic symmetry ev = A2 are vibronically square of the overlap of the vibrational wave functions, i.e.,
forbidden. to
Within the Born–Oppenheimer approximation, the elec-
tronic motion can be separated from the vibrational motion |

vib |

vib |2 (174)
226 Fundamentals of Electronic Spectroscopy

a quantity known as a Franck–Condon factor. Group- Herzberg–Teller coupling, or Herzberg–Teller intensity

theoretical arguments further lead to the conclusion that borrowing mechanism, and results from a breakdown of
the Franck–Condon factors are nonzero only if the Born–Oppenheimer approximation. The observation of
vibrational progressions following the selection rule (179)




vib ⊗ vib ⊇ A1 (or + ) (175) provides important information on vibronic coupling in that
it enables one to identify the modes responsible for the
For example, transitions from the ground vibrational level coupling.



of a molecule, which must have vib = A1 , are observable
only to totally symmetric vibrational levels of the final elec- Example


tronic state, i.e., to vibrational levels with vib = A1 . This
condition is fulfilled by all vibrational levels having only A1 ↔ A1 , B2 ↔ A1 , and B1 ↔ A1 transitions of C2v
even numbers of vibrational quanta in nontotally symmetric molecules are electronically allowed, but A2 ↔ A1 tran-
vibrational modes. More generally, equation (175) can be sitions are electronically forbidden in the electric-dipole
expressed as approximation. Such transitions may become observable by
vibronic coupling to electronic states of A1 , B2 , and B1
∆vi = vi
− vi

= 0, ±2, ±4, . . . (176) electronic symmetry induced by vibrational modes of A2 ,
B1 , and B2 symmetry, respectively.
for all nontotally symmetric vibrational modes i, and as
Specific selection rules, which depend on the point-group
∆vj = vj
− vj

= 0, ±1, ±2, . . . (177) symmetry of the molecular system under consideration,
can be derived from the general results presented above.
for all totally symmetric vibrational modes j . When the Such selection rules are now discussed in more detail, and
Born–Oppenheimer potential energy hypersurface of the separately, for atoms, diatomic (and linear) molecules and
two electronic states connected by an electronic transition polyatomic molecules in the next sections.
are identical, the observed transitions are characterized by When discussing selection rules of the kind presented
∆vi = 0 for all modes i, because of the orthogonality of the above, it is important to always keep in mind that all
vibrational wave functions (see Figure 42 in section 3.3.4). equations derived in this section are the result of approxi-
The observation of long vibrational progressions in elec- mations, approximations in the treatment of the interaction
tronic spectra indicates that the initial and final electronic between the atomic or molecular systems with the radi-
states have different equilibrium geometries and the length ation field, approximations concerning the separability of
of a progression in a given mode can be correlated to the the different types of motion, and approximations resulting
change of geometry along this mode. from the truncation of expansions. These approximations
are helpful in the interpretation of electronic spectra, but,
Electronically Forbidden but Vibronically Allowed Transi- often, a fully satisfactory treatment of intensity distributions
tions The second term of equation (172) becomes the makes it necessary to go beyond them, for instance, (i) by
dominant term when the transition is electronically forbid- considering the interaction between the rotational, vibra-
den. This term is nonzero if tional and electronic motions and the spin–orbit interaction,
(ii) by accounting for the fact that the normal modes of




vib ⊗ Qi ⊗ vib ⊇ A1 (or + ) (178) the initial electronic state do not always coincide with the
normal modes of the final electronic state, or even, in some
in which case one speaks of electronically forbidden but cases, (iii) by recognizing that the initial and final electronic
vibronically allowed transitions. Such transitions gain inten- states belong to different point groups.
sity by the vibronic coupling of the final electronic state to Point groups are convenient and adequate to discuss
another electronic state, which is connected to the initial vibronic selection rules in many molecular systems. Rovi-
electronic state by an electronically allowed transition. The bronic selection rules and selection rules in electronic
vibronic coupling is mediated by the nontotally symmetric transitions connecting electronic states subject to large-
normal mode with coordinate Qi . Consequently, observable amplitude motions or belonging to different point-group
vibronic transitions are characterized by symmetry are more conveniently treated in symmetry
groups representing the true symmetry properties of the
∆vi = vi
− vi

= 1, ±3, ±5, . . . (179) Hamiltonian describing the molecular system, such as
the complete-nuclear-inversion-permutation groups or the
and would be forbidden in an electronically allowed tran- molecular symmetry groups (Bunker and Jensen 1998). Fur-
sition. The vibronic coupling leading to the observa- ther information on such groups and their applications in
tion of electronically forbidden transitions is known as high-resolution spectroscopy are discussed in the articles by
 Fundamentals of Electronic Spectroscopy 227

Schnell 2011: Group Theory for High-resolution Spec- the transition moment
Ψ
|M̂i |Ψ

 with i = X, Y, Z can be
troscopy of Nonrigid Molecules, Oka 2011: Orders of expressed as
Magnitude and Symmetry in Molecular Spectroscopy
and Quack 2011: Fundamental Symmetries and Symme- 
⊗ 

⊇ Pu (180)
try Violations from High-resolution Spectroscopy, in this
handbook. Using the direct-product table (Table 2), this equation leads
to the selection rule known as Laporte rule:

∆L = L
− L

= 0, ±1 (0 ↔ 0 forbidden) (181)

3.2 Electronic Spectra of Atoms
and to
An immense body of data exists on the electronic spectra of
atoms. Extensive tables of atomic energy levels and tran- g ↔ u (g ↔ g and u ↔ u forbidden) (182)
sition frequencies have been published (see, for instance,
Moore 1949, 1952, 1958). Data exist on almost all atoms, Whenever electron-correlation effects are negligible and the
in almost all charge states. Rather than trying to recom- electronic wave function can be represented as a single
pile these data, this article introduces elementary aspects determinant (equation 15), absorption of a single photon
of the electronic spectra of atoms that are necessary to leads to a final electronic state differing from the initial
make good use of the published material. After a brief one by a single spin orbital, say φ  , so that the selection
summary of electric-dipole selection rules in Section 3.2.1, rules (181) and (182) reduce to
φ 
|M̂|φ 


the elementary aspects of electronic atomic spectroscopy
are illustrated in Section 3.2.2 with the examples of hydro- ∆ = 
− 

= ±1 (183)
gen and hydrogenlike atoms, alkali-metal atoms, and rare-
gas atoms. The first example was chosen because of the The same argumentation can easily be extended to the
immense importance of the spectrum of the H atom in the derivation of magnetic-dipole or electric-quadrupole selec-
development of quantum mechanics and electronic spec- tion rules as well as selection rules for multiphoton pro-
troscopy. It also gives an idea of the extreme precision of cesses.
spectroscopic measurements and how high-resolution elec-
tronic spectroscopy can be used to reveal the finest details 3.2.2 Selected Examples
of the energy level structure of atoms. The second example
Hydrogen and Other One-electron Atoms The spectra of
presents the electronic spectra of the alkali-metal atoms,
hydrogen and hydrogenlike atoms have been of immense
which were at the origin of the s, p, d, f,. . . nomencla-
importance for the development of quantum mechanics
ture used to label atomic states. Alkali-metal atoms play
and for detecting and recognizing the significance of fine,
a dominant role in current research in atomic physics. For
hyperfine, and quantum-electrodynamics effects. They are
instance, the knowledge of the fine and hyperfine struc-
also the source of precious information on fundamental
tures of selected transitions is required to understand laser
constants such as Rydberg’s constant and the fine-structure
cooling. With the electronic spectra of the rare-gas atoms,
constant. The desire to observe the spectrum of the H
we discuss atomic systems with more than one unpaired
atom at ever higher spectral resolution and to determine
electron, which have electronic states of different spin
the transition frequencies at ever higher accuracy has
multiplicity.
been one of the major driving forces in methodological
and instrumental developments in high-resolution electronic
3.2.1 Selection Rules spectroscopy.
If fine, hyperfine, and quantum-electrodynamics effects
Selection rules complementing the general ones already are neglected, the energy level structure of the hydrogen
presented in equations (160)–(165) can be derived using atom is given by equation (5) and is characterized by a
the point group Kh (Table 1) if the electron spin and high degree of degeneracy. The allowed electronic tran-
orbital motions can be separated, in which case ∆S = 0 sitions can be predicted using equation (183) and their
(equation 157). As mentioned in the previous section, the wavenumbers determined using equation (184)
laboratory-fixed reference frame is the only relevant frame
ν̃ = RM /n

− RM /n

2 2
when determining selection rules for atoms. The X, Y , (184)
and Z components of the electric-dipole-moment operator
M̂ transform as the Pu irreducible representation of Kh , which, for n

= 2, reduces to Balmer’s formula. The
so that the single-photon selection rules corresponding to transitions obeying the selection rule (183) are depicted
228 Fundamentals of Electronic Spectroscopy

schematically in Figure 32(a), in which, for simplicity, The degeneracies implied by equation (5) make the spec-
only transitions from and to the n = 1 and n = 2 lev- trum of the hydrogen atom and single-electron atoms sim-
els are indicated by double-headed arrows. Because of pler than the spectrum of other atoms at low resolution, but
their importance, many transitions have been given indi- more complex at high resolution. Precision measurements
vidual names. Lines involving n = 1, 2, 3, 4, 5, and have revealed the fine and hyperfine structure of many
6 as lower levels are called Lyman, Balmer, Paschen, lines of hydrogen and hydrogenlike atoms and even energy
Brackett, Pfund, and Humphrey lines, respectively. Above shifts resulting from the interaction of the atoms with the
n = 6, one uses the n value of the lower level to label zero-point radiation field, the so-called Lamb shifts (Lamb
the transitions. Lines with ∆n = n
− n

= 1, 2, 3, 4, 5, . . . and Retherford 1947). Today, the energy level structure of
are labeled α, β, γ , δ, φ, . . ., respectively. Balmer β, the hydrogen atom is known with exquisite precision (see
for instance, designates the transition from n = 2 to Figure 33, in which the level positions calculated with-
n = 4. The spectral positions of the allowed transitions out hyperfine structure from Mohr (2008) are given and
are indicated in the schematic spectrum presented in the fine and hyperfine structures are taken from Brod-
Figure 32(b). sky and Parsons (1967), Essen et al. (1971), Fischer et al.

E/hc

n=4
n=3

n=2

n=1
(a) s p d f g

∞ (ni = 9)

8000 7600 7200 6800 6400 6000

H ∞ (ni = 8) H H Pf ∞ (ni = 7) B

6000 5600 5200 4800 4400 4000

∞ (Humphrey) ∞ (Pfund)
Pf Pf B

4000 3600 3200 2800 2400 2000

Pa ∞ (Brackett) ∞ (Paschen) ∞ (Balmer) ∞ (Lyman)

2000 1600 1200 800 400 0

(b) Wavelength (nm)

Figure 32 (a) Energy level diagram of the H atom neglecting fine, hyperfine, and quantum-electrodynamics effects. Possible single-
photon transitions to and from the n = 1 and 2 levels are indicated by double-headed arrows. (b) Schematic spectrum of H showing
that the electronic spectrum extends from the microwave to the vacuum-ultraviolet ranges of the electromagnetic spectrum.
 Fundamentals of Electronic Spectroscopy 229

2P F=2
3/2 23′651.6(6) kHz
F=1

9′ 911′ 197.6(24) kHz

n=2
F=1
2S
1/2
177′ 556.8343(67) kHz

1′ 057′ 844.0(24) kHz F=0

2P F=1
1/2 59′169.6(6) kHz
(b)
F=0

2′ 466′ 061′ 413′ 187.080(25) kHz

F=1
2S
n=1 1/2
1′ 420′ 405.7517667(16) kHz

(a) F=0

Figure 33 Fine and hyperfine structure of the (a) n = 1 and (b) n = 2 levels of the hydrogen atom. Numerical values were taken
from Mohr (2008) for the positions without hyperfine structure and from Brodsky and Parsons (1967), Essen et al. (1971), Fischer et al.
(2004), Lundeen and Pipkin (1986), Kolachevsky et al. (2009), Mohr et al. (2008) for other intervals.

(2004), Lundeen and Pipkin (1986), Kolachevsky et al. µ+ and an electron), antimuonium (consisting of a negative
(2009), Mohr et al. (2008). The splitting of ≈ 0.0475 cm−1 muon µ− and a positron), etc., have the potential of pro-
of the 1s 2 S1/2 ground-state results from the hyperfine viding new insights into fundamental physical laws and
interaction. This splitting scales with n−3 and rapidly symmetries and their violations, such as those discussed
decreases with increasing n value, and also with increas- in Quack 2011: Fundamental Symmetries and Symme-
ing  value. The spin–orbit splittings, which are zero try Violations from High-resolution Spectroscopy, this
for s levels, are largest for p levels and also scale as handbook.
n−3 . The two components of the 2 P level with J = 1/2
and 3/2 are separated by ≈ 0.365 cm−1 . Dirac’s relativis- Alkali-metal Atoms A schematic energy level diagram
tic treatment predicts two components for n = 2, a lower, showing the single-photon transitions that can be observed
doubly degenerate spin–orbit level with J = 1/2 and an in the spectra of the alkali-metal atoms is presented in
upper, nondegenerate level with J = 3/2. The interaction Figure 34. The ground-state configuration corresponds to
with the zero-point radiation field removes the degener- a closed-shell rare-gas-atom configuration with a single
acy of the lower component and induces a splitting of valence n0 s electron with n0 = 2, 3, 4, 5, and 6 for Li,
≈ 0.0354 cm−1 . Na, K, Rb, and Cs, respectively. The energetic positions
High-resolution spectroscopy of hydrogenlike atoms, of these levels can be determined accurately from Ryd-
such as H, He+ , Li2+ , Be3+ , . . . and their isotopes contin- berg’s formula (equation 58). The Laporte selection rule
ues to stimulate methodological and instrumental progress (equation 181) restricts the observable single-photon transi-
in electronic spectroscopy. Measurements on “artificial” tions to those drawn as double-headed arrows in Figure 34.
hydrogenlike atoms such as positronium (consisting of an Neglecting the fine and hyperfine structures, their wave
electron and a positron), protonium (consisting of a proton numbers can be determined using equation (185):
and an antiproton), antihydrogen (consisting of an antipro-
ton and a positron), muonium (consisting of a positive muon ν̃ = RM /(n

− δ

)2 − RM /(n
− δ
)2 (185)
230 Fundamentals of Electronic Spectroscopy

E/hc defects of the sodium atom are δs ≈ 1.35, δp ≈ 0.86, δd ≈

0.014, and δf ≈ 0, so that the lowest frequency line of
(n 0 + 2)f the principal series (called the sodium D line because
(n 0 + 2)s
(n 0 + 1)p (n 0 + 1)d it is a doublet, see below) lies in the yellow range of
(n 0 + 1)s
the electromagnetic spectrum, and not in the VUV as
does Lyman α. The fact that the n0 p ← n0 s lines of
Principal series
the alkali-metal atoms lie in the visible range of the
n 0p Sharp series
electromagnetic spectrum makes them readily accessible
Diffuse series
with commercial laser sources, and therefore extensively
Fundamental series
studied and exploited in atomic-physics experiments.
Most transitions of the alkali-metal atoms reveal fine and
n 0s hyperfine structures. As in the case of H, the hyperfine-
s p d f structure splittings are largest in the ground state (3s 2 S1/2
in the case of Na) and the fine-structure splittings are largest
Figure 34 Schematic diagram showing the transitions that can in the lowest lying p level (3p 2 PJ with J = 1/2, 3/2 in
be observed in the single-photon spectrum of the alkali-metal
the case of Na). The details of the structure of these two
atoms.
levels of Na are presented in Figure 35. At low resolution,
the 3p←3s line appears as a doublet with two components
The deviation from hydrogenic behavior is accounted for at 16 960.9 and 16 978.1 cm−1 , separated by an interval of
by the -dependent quantum defects. Transitions from (or 17.2 cm−1 corresponding to the spin–orbit splitting of the
to) the lowest energy levels can be grouped in Rydberg 3p state. The second largest splitting (≈ 0.06 cm−1 ) in the
series, which have been called principal, sharp, diffuse, and spectrum arises from the hyperfine splitting of 1772 MHz of
fundamental. Comparing Figure 34 with Figure 32, one can the 3s state. Finally, splittings of less than 200 MHz result
see that the principal series of the alkali-metal atoms (called from the hyperfine structure of the 3p levels.
principal because it is observed in absorption and emission) The level structures depicted in Figure 35 are character-
corresponds to the Lyman lines of H, the diffuse and sharp istic of the n0 p← n0 s transitions of all alkali-metal atoms,
series to the Balmer lines, and the fundamental series to the which are nowadays widely used in the production of cold
Paschen lines. and ultracold atoms by laser cooling. Laser-cooling exper-
The quantum defects are only very weakly dependent iments exploit closed transitions and achieve a reduction
on the energy. Neglecting this dependence, the quantum of velocity of the sample in the direction opposite to the

F=3
60 MHz
3p 2P3/2 F = 2 36 MHz
F = 1 16 MHz
F=0

17.19 cm−1 = 515.4 GHz

F=2
3p 2P1/2
188 MHz
F=1

16 960.9 cm−1

F=2

3s 2S1/2
1772 MHz

F=1

Figure 35 Schematic diagram showing the fine and hyperfine structures of the 3s and 3p levels involved in the lowest frequency line
of the principal series of 23 Na.
 Fundamentals of Electronic Spectroscopy 231

laser propagation direction as a result of a large number of 2P

1/2
subsequent absorption–emission cycles. If a narrow-band
laser is tuned to the low-frequency side of a spectral line,
only atoms with a positive Doppler shift, i.e., atoms mov-
ing toward the laser light source can absorb radiation. By
doing so, they also acquire a momentum
k (k = 2π/λ) in 2P
3/2

the direction opposite to their motion, which reduces their

velocity. Spontaneous re-emission of the absorbed photons
occurs with an isotropic probability distribution so that,
on average, the momentum of the atoms is reduced by
k
per absorption–emission cycle. Several thousand cycles are
required to stop a sodium atom initially leaving an oven in
an effusive beam.
The efficiency of the cooling process is reduced if the
optical cycle is not closed, i.e., if spontaneous emission (n + 2)s[3/2]1 n d[1/2]1 n d[3/2]1 (n + 2)s'[1/2]1 n d'[3/2]1
can populate other hyperfine levels of the ground state.
Inspection of Figure 35 leads to the conclusion that only Figure 36 Schematic diagram showing Rydberg series converg-
two of the 10 possible hyperfine components of the 3p ing to the two spin–orbit components 2 PJ (J = 1/2, 3/2) of the
2 P ← 3s 2 S rare-gas atomic ions Rg+ . The series are designated in Racah
1/2 transition correspond to closed transitions,
J
notation as n(
) [k]J , the
-sign designating series converging on
the F
= 3 ← F

= 2 and the F
= 0 ← F

= 1 compo- the upper (2 P1/2 ) ionization threshold. Interaction between series
nents. Near-resonant excitation of the F
= 1 and 2 hyper- is represented by horizontal arrows.
fine components, however, occasionally leads to emission
to the F

= 1 and F

= 2 levels, which lie too far from
the F
= 3 ← F

= 2 and the F
= 0 ← F

= 1 transi- electrons, which leads to both S = 0 and S = 1 states.
tions, respectively, for further efficient absorption, so that Moreover, these states form Rydberg series that converge
the optical cycling is terminated. This problem is usually on two closely spaced ionization limits corresponding
overcome by repumping the F

= 1 or the F

= 2 level to the two spin–orbit components (J + = 1/2, 3/2) of
with other lasers. The efficiency of the laser-cooling pro- the 2 PJ + ground state of Rg+ , rather than on a single
cess can also be increased by using circularly polarized ionization limit, as is the case for H and the alkali-metal
radiation, exploiting the selection rules (163) and (164). atoms. This situation, which is encountered in most atoms,
These considerations illustrate the importance of high- results in spectrally more dense spectra with pronounced
resolution spectroscopic measurements of electronic transi- perturbations. Figure 36 depicts schematically the J = 1
tions in atoms and the understanding of their structures, Rydberg series of the rare-gas atoms located below the 2 PJ +
without which important applications would never have (J + = 1/2, 3/2) ionization thresholds that are optically
been developed. Indeed, to fully exploit the potential of accessible from the 1 S0 ground state.
laser cooling, a very detailed knowledge of the fine and Two angular momentum coupling schemes are used to
hyperfine structures of electronic transitions is mandatory. label these Rydberg states. The first one corresponds to
If one desires to load the cold atoms in traps, it is also nec- the familiar LS-coupling scheme discussed in Section 2.1.4
essary to study the effects of electric and magnetic fields and tends to be realized, if at all, only for the lowest
on the hyperfine-structure levels. For further details on laser Rydberg states and the lightest atoms. Five series are
cooling, the reader is referred to the article by Metcalf and optically accessible, two s series ((n0 p)5 (ns)1 3 P1 and
1
van der Straten (2003). P1 ) and three d series ((n0 p)5 (nd)1 3 D1 , 3 P1 , and 1 P1 ).
The second one is a variant of the jj coupling scheme
Rare-gas Atoms The 1 S0 ground state of the rare-gas and becomes an increasingly exact representation at high
atoms (Rg = Ne, Ar, Kr, and Xe) results from the full- n values, when the spin–orbit coupling in the 2 PJ + ion
shell configurations [. . .](n0 p)6 with n0 = 2, 3, 4, and 5 for core becomes stronger than the electrostatic (including
Ne, Ar, Kr, and Xe, respectively. Single-photon absorption exchange) interaction between the Rydberg and the core
by electrons in the (n0 p)6 orbitals leads to the excitation electrons. As a result, the core and Rydberg electrons
of J = 1 states of the configurations [. . .](n0 p)5 (ns)1 and are decoupled, and J + becomes a good quantum number
[. . .](n0 p)5 (nd)1 . instead of S. In this labeling scheme, the states are
Compared to H and the alkali-metal atoms discussed designated (2 PJ + )n[k]J , k being the quantum number
in the previous examples, the lowest excited electronic resulting from the addition of J+ and
. The five optically
configurations contain two, instead of only one, unpaired accessible J = 1 series are labeled ns[3/2]1 , ns
[1/2]1 ,
232 Fundamentals of Electronic Spectroscopy

B C

160

180

200
55d[1/2]1

55d[3/2]1

56d[1/2]1

56d[3/2]1
57s[3/2]1

58s[3/2]1
n*

Ion signal (arbitrary units)

127 073 127 073.5 127 074 127 074.5 127 102 127 104 127 106
−1 −1
Wave number (cm ) Wave number (cm )

A
Ion signal (arbitrary units)

(in B) (in C)

120
40

50

60

80

n*

127 020 127 040 127 060 127 080 127 100
(a) Wave number (cm−1)

0.8

0.6
Ion signal (arbitrary units)

0.4
23s

24s

25s

26s
21d

0.2
22d

23d

24d

0.0
128 290 128 300 128 310 128 320 128 330 128 340 128 350
(b) Wave number (cm−1)

Figure 37 High-resolution VUV laser spectra of Ar recorded with a narrow-band laser. (a) Region below the 2 P3/2 ionization threshold
showing the perturbed ns/d[k]J =1 series. The spectra labeled B and C represent sections of the spectrum labeled A presented on an
enlarged scale. (b) Region above the 2 P3/2 threshold revealing the broad asymmetric nd
[3/2]1 , and the narrow, symmetric ns
[1/2]1
resonances. [Adapted from Hollenstein (2003) Erzeugung und spektroskopische Anwendungen von schmalbandiger, kohärenter, vakuum-
ultravioletter Strahlung, PhD thesis, Eidgenössische Technische Hochschule Zürich, ETH Zürich, CH-8093 Zürich, Switzerland, Diss.
ETH Nr. 15237.]
 Fundamentals of Electronic Spectroscopy 233

nd[1/2]1 , nd[3/2]1 , nd
[3/2]1 , the “prime” being used to to the S = 0 ground state is strongly forbidden by single-
designate the two series converging to the 2 P1/2 ionization photon electric-dipole selection rules. Consequently, these
limit (Figure 36). states are very long-lived, so that, for many purposes, they
The interactions between the series converging to the can be used in experiments as if they were stable ground-
different ionization limits lead to pronounced perturbations state atoms: their long lifetimes enable precision measure-
below the 2 P3/2 ionization limit and to the autoionization ments, they give access to spectroscopic investigation of
of the ns
and nd
series in the energetic region between other S = 1 states, they can be laser cooled using closed
the 2 P3/2 and 2 P1/2 ionization limits. Because of the transitions in the triplet manifold of states, they can be used
series interactions, the spectral positions are not accurately in reactive scattering experiments, etc.
described by Rydberg’s formula, but are best described by
multichannel quantum defect theory (Lee and Lu 1973; see 3.2.3 Stark and Zeeman Effects in Atomic Spectra
also Jungen 2011a: Elements of Quantum Defect Theory,
this handbook). When considering the effects of static electric and magnetic
Several sections of the single-photon VUV spectrum of fields on electronic transitions, it is convenient to discuss
Ar are presented in Figure 37. Figure 37(a) corresponds to the effects of these fields on the selection rules and on the
the region where Rydberg states of principal quantum num- spectral positions separately. The effects of magnetic and
ber n ≥ 33 below the 2 P3/2 ionization limit can be excited electric fields on the energy level structure of atoms have
from the ground state. In the region below 127 060 cm−1 , been described in Sections 2.1.7 and 2.1.8, respectively.
only the nd[3/2]1 and ns[3/2]1 carry intensity. These two We therefore focus here on the selection rules and their
series are almost degenerate. The splittings can hardly be manifestations in electronic spectra of atoms.
seen on the wave-number scale used to draw the spectrum, In the presence of a homogeneous electric (or magnetic)
but are clearly visible on the expanded scale of the spec- field, the symmetry of space is reduced from spherical
trum labeled B, which corresponds to the region of principal (isotropic) to cylindrical. Consequently, the total angular
quantum number around n = 55. The high-n region of the momentum quantum number J (or F ) ceases to be a good
spectrum is also displayed on an enlarged scale in the spec- quantum number, the only good quantum number being
trum labeled C. The nd[1/2]1 series is extremely weak at n the magnetic quantum number MJ (or MF ) associated with
values below 50, but becomes the dominant series beyond the projection of J (F) along the direction of the field
n = 80. In an unperturbed Rydberg series, the intensity vector. The Z axis of the laboratory-fixed reference frame
should decrease as n−3 , as explained in Section 2.1.6. The is commonly chosen to lie parallel to the static field vector,
anomalous intensity distribution of the nd[1/2]1 series has i.e., E = (0, 0, E) and B = (0, 0, B).
its origin in the interactions with the series converging to the The electric-dipole selection rules depend on the relative
2P orientation of the polarization vector of the radiation field
1/2 ion core, which are such that, in some spectral regions,
it has almost pure S = 1 character and cannot be excited and the static field vector. If the radiation is linearly
from the S = 0 ground state. Figure 37(b) displays a section polarized with polarization vector perpendicular to the static
of the VUV spectrum of Ar in the region between the 2 P3/2 field vector, then
and 2 P1/2 ionization limits. The ns
[1/2]1 and nd
[3/2]1
series appear as sharp, symmetric, and broad, asymmetric ∆MJ = ±1 (or ∆MF = ±1) (186)
autoionization resonances in this region, respectively.
The VUV absorption spectra of Ne, Kr, and Xe are in which case one speaks of a σ configuration, from the
qualitatively similar to that of Ar. Ne, Kr, and Xe all have German word “senkrecht” (= perpendicular), replacing the
several isotopes, some of which have a nonzero nuclear spin first letter by its Greek equivalent, s → σ. If the radiation
and a hyperfine structure. The hyperfine structures in the is linearly polarized with polarization vector parallel to the
VUV absorption spectrum of 83 Kr, 129 Xe, and 131 Xe appear static field vector, then
complex at first sight but can be quantitatively described
by MQDT using the same series-interaction parameters as ∆MJ = ±0 (or ∆MF = ±0) (187)
the I = 0 isotopes (Wörner et al. 2003, 2005, Schäfer and
Merkt 2006, Paul et al. 2009, Schäfer et al. 2010; see also and the configuration is referred to as π (from the German
discussion of spin–orbit and hyperfine autoionization in word “parallel”, p → π). The use of circularly polarized
Section 3.5.1). radiation leads to the most restrictive selection rule on MJ
The fact that several low-lying levels of the rare-gas (MF ) if the radiation propagates in a direction parallel to
atoms have almost pure S = 1 character results in the the static field vector, in which case one has either
metastability of these levels. The radiative decay of the
lowest electronically excited S = 1 state with J = 0 and 2 ∆MJ = 1 (∆MF = 1) (188)
234 Fundamentals of Electronic Spectroscopy

or rules (186)–(189), 10 lines can be observed with the

different polarization arrangements. Because the Zeeman
∆MJ = −1 (∆MF = −1) (189) splittings now depend on the values of L, S, and J , the
spectral patterns are characteristic of the terms involved
depending on the helicity. in the electronic transitions, which can be used to assign
them.
Magnetic Fields and Zeeman Effect Because the elec-
tron Zeeman effect is much larger than the nuclear Zee- Electric Fields and Stark Effect To illustrate the effect
man effect, we consider here only the influence of the of electric fields on atomic spectra, we first discuss the
former on electronic transitions of atoms. If the states Stark effect in the Lyman α transition of H. The Stark
connected by the transitions are singlet states (S = 0), effect leads to a coupling of the closely spaced n = 2 s and
the Zeeman effect arises solely from the orbital motion p states, which are split at zero field by the Lamb shift and
and particularly simple spectral structures result (Figure 8 the spin–orbit interaction (Figure 33). Figure 40(a) and (b)
and equations 60 and 61 describing the normal Zeeman depict the calculated electric-field dependence of the n = 2
effect). Equation (61) implies that, in this case, the fre- energy levels, and VUV spectra of the Lyman α line of H
quency intervals between neighboring Zeeman levels are recorded in a field of 5465 V cm−1 , respectively, as reported
the same (µB B/ h) in the lower and upper electronic states. by Rottke and Welge (1986).
The transitions allowed by the selection rules (186)–(189) Because of the near degeneracy of these levels, the Stark
are indicated in Figure 38(a) and (b) for 1 S0 ↔ 1 P1 and effect rapidly becomes linear with increasing electric field,
1
P1 ↔ 1 D2 transitions, respectively, from which one sees but a fine structure remains noticeable. In the absence
that only three lines can be observed, two in σ and one of fine-structure splittings, the Stark level structure would
in π polarization configuration, separated by a frequency consist of three levels (Figure 11): two outer components
interval of µB B/ h. The schematic spectra displayed in with m = 0 corresponding to the |n1 , n2 , |m | = |1, 0, 0
Figure 38(c) illustrate the fact that the appearance of the and |0, 1, 0 Stark states, i.e., to values of k of ±1,
spectra is entirely determined by the polarization configu- and one central component corresponding to the |0, 0, 1
ration and does not depend on the L value of the states Stark state. With the selection rules for σ (∆m = ±1)
involved in the transition. and π (∆m = ±0) polarization configurations, one would
The situation is more complicated in S ≥ 1/2 states expect to see either the central |0, 0, 1 component (σ
because, in this case, the Zeeman effect is anomalous and configuration) or the |1, 0, 0 and |0, 1, 0 components
the Zeeman level shifts are given by equation (63) and (π configuration). This expectation corresponds to the
depend on the values of L, S, and J via the dependence of experimental observations, which, however, also reveal
gJ on these quantum numbers (equation 52). For example, fine-structure effects and weak lines corresponding to
Figure 39 illustrates the case of a 2 S1/2 ↔ 2 PJ (J = the “forbidden” Stark components. These components are
1/2, 3/2) transition, for which, according to the selection observed because mj , rather than m , is the good quantum

2
1 1
1 0 1D
P1 2 0 n
−1 −1
−2
mBB n
s p s p s h

n
1
1 1P
S0 0 1 0
−1
(a) ML (b) ML (c)

Figure 38 The normal Zeeman effect in the electronic spectrum of atoms. (a) 1 S0 ↔ 1 P1 transition, (b) 1 P1 ↔ 1 D2 transition, and (c)
schematic representation of the spectra.
 Fundamentals of Electronic Spectroscopy 235

3/2

1/2
2P
gJ = 4/3 4mBB n
3/2
3h
−1/2
n
σ
n3/2 −3/2
n
π
n
π σ (b) n1/2 n3/2

2P
gJ = 2/3 1/2 2mBB
1/2
−1/2 3h
n1/2

1/2

2S
gJ = 2 2mBB
1/2
h
−1/2
(a) MJ

Figure 39 The anomalous Zeeman effect in a 2 S1/2 ↔ 2 PJ (J = 1/2, 3/2) transition: (a) energy level diagram in which the allowed
transition for π and σ polarization configurations are indicted and (b) schematic representation of the spectra.

number when spin–orbit coupling is considered, and also et al. 1979), rare-gas atoms (Ernst et al. 1988, Brevet
because the polarization of the VUV laser radiation was not et al. 1990, Grütter et al. 2008)), and even molecules (e.g.,
perfectly linear, as discussed by Rottke and Welge (1986). H2 , (Fielding and Softley 1991, Hogan et al. 2009)). The
In Rydberg states of atoms and molecules, the Stark effect strong field dependence of the outer members of the linear
leads to very characteristic spectral structures. Figure 41 Stark manifolds is indicative of very large electric-dipole
presents π-polarized VUV laser spectra of transitions from moments, which have been recently exploited to decelerate
the 1 S0 ground state of Ar to Stark states belonging to beams of Rydberg atoms and molecules (Procter et al.
the n = 22 (MJ = 0) manifold of states located below the 2003, Vliegen et al. 2004) and to load cold Rydberg atom
2
P3/2 ground state of Ar+ (Vliegen et al. 2004). The spectra and molecule samples in electric traps (Vliegen et al. 2007,
recorded at different fields have been shifted along the verti- Hogan et al. 2009). High-resolution electronic spectroscopy
cal axis, so that the origins of their intensity scale coincide of Rydberg Stark states in cold, high-density samples has
with the values of the electric field (in volt per centime- also been used to study dipole–dipole interactions between
ter) used to record them. At low fields (bottom spectra), neighboring Rydberg atoms (Mourachko et al. 1998).
the optically allowed J = 1 series converging to the 2 P3/2
ground state of Ar+ (23d[1/2]1 , 24s[3/2]1 , and 23d[3/2]1 )
are observed. As the field increases, transitions to the 24 and 3.3 Electronic Spectra of Diatomic Molecules
25 p[1/2]0 levels gain intensity by Stark mixing with the d
levels following the Stark-mixing selection rule ∆ = ±1 This section describes elementary aspects of the electronic
(see equation 67). Stark mixing also takes place with the f spectra of diatomic molecules, with emphasis on selection
levels, which are almost degenerate with the  ≥ 4 levels rules and the overall structure of electronic transitions.
and form with them a manifold of states subject to a linear
Stark effect. This high- manifold of Stark states becomes
3.3.1 Selection Rules
the dominant spectral pattern at high fields.
Series of spectra such as those presented in Figure 41 Theset of selectionrules presented in equations (160)–(165)
are referred to as Stark maps and have been recorded can be extended by considering those that can be derived
for many atoms (e.g., alkali-metal atoms (Zimmerman using the point groups D∞h for homonuclear diatomic
236 Fundamentals of Electronic Spectroscopy

|1,0,0〉|±½〉 5465 V cm−1

30 2
P3/2 |ml |=3/2
π 2
S1/2 |ml |=1/2
|0,0,1〉
2
|0,0,1〉
P3/2 |ml |=1/2
20
σ
σ |0,0,±1〉|±½〉

Electron signal
10
Energy (GHz)

2
P3/2 |ml |=3/2 0
5465 V cm−1
0 2
S1/2 |ml |=1/2 σ |0,0, 1〉|±½〉
2 2
P3/2 |ml |=1/2 P1/2 |ml |=1/2
−10 |1,0,0〉 |0,1,0〉

2
P1/2 |ml |=1/2
−20 π
π
|0,1,0〉|±½〉
−30
0

0 2 4 6 8 10 −40 0 +40
(a) Electric field strength (kV cm−1) (b) Detuning (GHz)

Figure 40 (a) Stark effect in the n = 2 levels of H. At low electric fields, the levels are labeled with the usual term symbols. At
high fields, the levels are labeled using the parabolic quantum numbers n1 , n2 , and m defined in Section 2.1.8 as |n1 , n2 , |m ||mS .
The vertical dashed line indicates the field used for the measurements presented in panel (b), and σ and π designate the levels that
can be excited from the 1 2 S1/2 level using σ and π polarization configurations, respectively. (b) Experimental spectra of the Lyman
α line of atomic hydrogen recorded in σ (top spectrum) and π (bottom spectrum) polarization configurations. Each line is labeled by
the parabolic quantum numbers |n1 , n2 , |m | and by the dominant contribution to the wave function of the n = 2 level. The hyperfine
structure is not resolved in the experiment. [Adapted from Rottke and Welge (1986).]

molecules, and C∞v for heteronuclear diatomic molecules. as the representation of the C∞v group), and Tz trans-
In diatomic molecules, the vibronic symmetry ev = forms as + +
g (or ), equations (192) and (193) can be
elec ⊗ vib is always equal to the electronic symmetry elec written as
because the only vibrational mode is totally symmetric


elec


⊗ elec ⊇ +
(u) (194)
vib = +
g for D∞h (190)
in which case the transition moment lies parallel to the
and internuclear (z) axis and one speaks of a parallel transition,
and
vib = + for C∞v (191)



elec ⊗ elec ⊇ (u) (195)

Electronically forbidden transitions are, therefore, necessar- respectively, in which case the transition moment lies
ily also vibronically forbidden (see equations 173 and 178). perpendicular to the internuclear (i.e., along the x or y) axis
Electronically allowed transitions fulfill either and one speaks of a perpendicular transition. Evaluating
equations (194) and (195) using the direct-product table


elec


⊗ (Tz ) ⊗ elec ⊇ +
(g) (192) (Table 9) leads to the selection rules

or ∆Λ = 0 (u ↔ g) (196)

elec


⊗ (Tx,y ) ⊗ elec ⊇ +
(g) (193) for parallel transitions and

where the (g) subscripts only apply to homonuclear ∆Λ = ±1 (u ↔ g) (197)

diatomic molecules. Because Tx and Ty transform as the
u irreducible representation of the D∞h point group (or for perpendicular transitions.
 Fundamentals of Electronic Spectroscopy 237

126 875.0 126 876.0

348
k = −19 k = −17 k = −15
344

340

400

300
Intensity (arb. units)

200

c c′
100
b
a
b′
a′
0
126 870.0 126 880.0 126 890.0
Wave number (cm−1)

Figure 41 Stark effect in the n = 22, MJ = 0 levels of Ar located below the 2 P3/2 ground state of Ar+ . The spectra recorded at
different fields have been shifted along the vertical axis so that the origins of their intensity scale coincide with the values of the
electric field (in volts per centimeter) used to record them, from bottom to top 0, 70, 136, 204, 272, and 340 V cm−1 . The linear high-
Stark manifold is situated between the dotted lines. The states labeled a, a
, b, b
, c, c
, and d correspond to the 22d[1/2]1 , 23d[1/2]1 ,
22d[3/2]1 , 24s[3/2]1 , 23p[1/2]0 , 24p[1/2]0 , and 24p[1/2]2 states, respectively. The top panel shows the fine structure of three Stark
states with k = −19, −17, and −15, where k represents the difference n1 − n2 . [Adapted from Vliegen et al. (2004).]

Examples for parallel transitions and

In D∞h molecules, + +
g ↔ u , g ↔ u ,. . . transitions ∆Ω = ±1 (u ↔ g) (199)
are allowed parallel transitions, and + +
g ↔ u , u ↔
g , g ↔ ∆u , u ↔ ∆g , . . . are allowed perpendicular
for perpendicular transitions (see also below).
transitions.
Additional selection rules are given by equations (157) 3.3.2 Forbidden Electronic Transitions
and (158). As stated above, the ∆MJ selection rule depends
on the polarization of the radiation field. When the elec- Electronically (and vibronically) forbidden single-photon
tronic states involved in the transition are not well described transitions in diatomic molecules may nevertheless be
by Hund’s angular momentum coupling cases (a) or (b), observable experimentally. Such transitions can be classi-
but rather by Hund’s case (c), the ∆S = 0 selection rule fied into two categories.
no longer applies, and Λ must be replaced by Ω in
1. Magnetic-dipole and Electric-quadrupole Transi-
equations (196) and (197), i.e.,
tions
Absorption results from the interaction of the electro-
∆Ω = 0 (u ↔ g) (198) magnetic radiation field with the magnetic-dipole or the
238 Fundamentals of Electronic Spectroscopy

Table 19 Character table of the extended C(2)

∞v point group.

C(2)
∞v E 2Cϕ∞ 2C2ϕ
∞ 2C3ϕ
∞ ... ∞σv R 2Cϕ∞ R ...

+ (= A1 ) 1 1 1 1 . . . 1 1 1 ... z
− (= A2 ) 1 1 1 1 . . . −1 1 1 ... Rz
(= E1 ) 2 2 cos ϕ 2 cos(2ϕ) 2 cos(3ϕ) . . . 0 2 2 cos ϕ ... x, y; Rx , Ry
∆(= E2 ) 2 2 cos(2ϕ) 2 cos(4ϕ) 2 cos(6ϕ) . . . 0 2 2 cos(2ϕ) ...
(= E3 ) 2 2 cos(3ϕ) 2 cos(6ϕ) 2 cos(9ϕ) . . . 0 2 2 cos(3ϕ) ...
... ... ... ... ... . . . ... ... ... ...
E1/2 2 2 cos(ϕ/2) 2 cos ϕ 2 cos(3ϕ/2) . . . 0 −2 −2 cos(ϕ/2) ...
E3/2 2 2 cos(3ϕ/2) 2 cos(3ϕ) 2 cos(9ϕ/2) . . . 0 −2 −2 cos(3ϕ/2) ...
E5/2 2 2 cos(5ϕ/2) 2 cos(5ϕ) 2 cos(15ϕ/2) . . . 0 −2 −2 cos(5ϕ/2) ...
... ... ... ... ... . . . ... ... ... ...

The character table of the extended D(2)

∞h point group can be obtained from the D∞h point group by making the corresponding changes.

electric-quadrupole moment of the molecule. Since the Table 20 Transformation properties of the electron-spin func-
(x, y, z) components of the magnetic-dipole moment tions in the extended point group D(2)
∞h .
transform as the rotations Rx , Ry , and Rz and the com-
ponents of the quadrupole moment transform as (α ij ) S 0 1/2 1 3/2 ...
(see Tables 7 and 8), the corresponding selection rules
S +
g E1/2,g −
g + g E1/2,g + E3/2,g ...
can be derived as in the case of an electric-dipole transi-
tion. The selection rule for magnetic-dipole transitions The transformation properties in the extended point group C(2)
∞v can be
is thus obtained by disregarding the subscript g.

i ⊗ (Rα ) ⊗ f ⊇ +
(g) with α = x, y, z (200) double group is represented in Table 19, and Table 20
shows how the electron-spin functions transform in the
and that for electric-quadrupole transitions is D(2) (2)
∞h and the C∞v point groups. The symmetry es of
the electronic wave functions (now including electron
i ⊗ (α (ij ) ) ⊗ f ⊇ +
(g) (201) spin) can be determined from the product

Example es = elec ⊗ espin (202)

1
+ 1 −
g ↔ g transitions are electric-dipole-forbidden,
but magnetic-dipole-allowed transitions, because Rz which can be evaluated using the transformation
transforms as −g in D∞h molecules (Table 8).
properties of the electron-spin functions summarized
2. Intercombination Transitions in Table 20. An intercombination transition is only
Intercombination transitions violate the ∆S = 0 selec- observable if equation (203) is fulfilled instead of
tion rule (equation 157). Such transitions mainly occur equations (192) and (193):
in molecules possessing a significant spin–orbit inter-
action. In this case, Hund’s angular momentum cou-


es


⊗ (Tα ) ⊗ es ⊇ +
(g) with α = x, y, z (203)
pling cases (a) and (b), upon which the selection
rules (196) and (197) rely, are no longer a perfect Example
description, and neither Σ nor Λ are good quantum We consider the electronically forbidden 1 + g →
numbers. 3
u transition with ∆S = 1 (singlet-triplet transi-
When the spin–orbit interaction is dominant, a Hund’s tion). With the help of Tables 19, 20, and 9, one
case (c) nomenclature is more appropriate and the obtains es


= +



g and es = elec ⊗ espin = u ⊗
− + −
selection rules (198) and (199) must be used instead ( g + g ) = u + u + u + ∆u . The transforma-
of the selection rules (196) and (197). When the tion properties of Tx,y,z in D∞h imply that only the u
spin–orbit interaction is weak, so that Hund’s case and + 3
u components of the u state can be accessed
(a) or (b) representations remain good approximations, from an initial state of symmetry 1 +g . Alternatively,
group-theoretical arguments can still be used to pre- one may choose to express the selection rules in Hund’s
dict which intercombination transitions are observable, coupling case (c) as ∆Ω = 0, ±1, which does not
but spin double groups are required for this task (see necessitate the specification of the total electron-spin
Section 2.3.3). The character table of the C(2)∞v spin quantum number S.
 Fundamentals of Electronic Spectroscopy 239

V (R ) V (R )

Re Internuclear distance R Re Internuclear distance R

0–0 3–0 4–0

2–0 5–0
1–0

1–0 0–0

(a) Transition energy (b) Transition energy

Figure 42 Illustration of the Franck–Condon principle for (a) an electronic transition between two electronic states having almost
identical Born–Oppenheimer potential energy functions and (b) an electronic transition between two electronic states with Re

<< Re
.
The shaded areas represent the regions where the vibrational wave function of the initial state has a significant amplitude. The spectra
displayed below the potential energy diagrams represent schematically the expected appearance of electronic spectra recorded from the
v = 0 level of the lower electronic state.

3.3.3 Vibronic Structure and the Franck–Condon Figure 42(a), the Born–Oppenheimer potential energy func-
Principle tions of the two electronic states are almost identical. In this
case, vibrational wave functions of the same vibrational
Equation (172) implies that the intensity Iα
,v
,α

,v

of a quantum number (v
= v

) are also almost identical in the
transition between two vibronic states should be approx- two electronic states. The orthogonality of the vibrational
imately proportional to the square of the overlap integral wave functions implies the selection rule ∆v = 0 and the


vib |

vib  of the vibrational wave functions: electronic spectrum consists of a single dominant vibra-
tional band corresponding to the v
= 0 ← v

= 0 band
(labeled 0-0 in the spectrum drawn at the bottom of the
Iα
,v
,α

,v

∝ |

vib |

vib |2 = |
v
|v

|2 (204)
figure).
In Figure 42(b), the potential energy functions of the two
The square of the integral

vib |

vib , which is called states differ from each other. The equilibrium internuclear
the Franck–Condon factor (see Section 3.1), thus indicates separation Re
of the upper potential function is larger
how the intensity of an electronically allowed transition than that of the lower state. Consequently, transitions
between the electronic states α

and α
is partitioned among originating from the v

= 0 level of the lower electronic
the various vibrational bands. state can access several vibrational levels of the upper
Figure 42 shows two schematic illustrations of the state. The Franck–Condon factors are, therefore, nonzero
Franck–Condon principle applied to the absorption spec- in the energetic region where the repulsive part of the
trum of diatomic molecules in their ground state. In upper potential energy function lies vertically above the
240 Fundamentals of Electronic Spectroscopy

region where the ground-state vibrational function has parities. The parities of rovibrational levels of diatomic
a nonzero amplitude. The expected vibrational structure molecules can be determined using equation (109) and
of the corresponding band is represented schematically are indicated in the energy level diagrams presented in
below the potential energy diagram and extends beyond Figure 19.
the dissociation limit of the upper electronic state where Combined with the generalized Pauli principle, the con-
the spectrum becomes continuous. The shaded areas in servation of nuclear-spin symmetry implied by the second
Figure 42 represent the regions where the vibrational wave factor of equation (156) leads to a further selection rule for
function of the initial state has a significant amplitude. They homonuclear diatomic molecules:
help to see which vibrational levels of the final state are
accessible from the ground state. s ↔ s, a↔a (s ↔ a forbidden) (205)
Franck–Condon factors represent an approximation of
the relative intensities, which relies on the assumption where the “s” and “a” labels indicate whether the rovi-
that the electronic transition moment does not vary with
bronic wave function is symmetric or antisymmetric with
internuclear separation, at least not over the range where
respect to permutation of the coordinates of the identical
the relevant vibrational functions have significant ampli-
nuclei, respectively. If the nuclei are bosons (fermions),
tudes. Given that diatomic molecules have zero dipole
rovibronic wave functions of “a” symmetry combine with
moments both in the separated-atoms and the united-atoms
nuclear-spin functions of “a” symmetry (“s” symmetry),
limits, the dipole-moment function must go through at
whereas rovibronic wave functions of “s” symmetry com-
least one maximum at intermediate distances. Neglect-
bine with nuclear-spin wave functions of “s” symmetry (“a”
ing its variation with R thus represents an approx-
symmetry). For a given value of the nuclear-spin quantum
imation, and indeed it is often necessary to include
number I of the identical nuclei, the numbers Ns and Na of
higher terms than the first in equation (171) to prop-
symmetric and antisymmetric nuclear-spin wave functions,
erly account for the vibrational intensity distribution of
respectively, are given by
an electronic spectrum. The dependence of the electric-
dipole moment on the nuclear geometry has the largest
(2I + 1)2 + (2I + 1)
consequences in the spectra of polyatomic molecules, Ns = and
because it can lead to the observation of electronically 2
forbidden transitions, as explained in Section 3.1 and (2I + 1) − (2I + 1)
2
Na = (206)
illustrated in Section 3.4.2 by the electronic spectrum of 2
benzene.
and are refered to as nuclear-spin statistical factors. The
parity (±) and permutation (a/s) symmetry of the rovi-
3.3.4 Rovibronic Structure
brational levels of the most common electronic states
The description of the rotational structure of electronic tran- are indicated in the energy level diagrams presented in
sitions requires the parity selection rule (equation 165) and Figure 19. 16 O, for instance, is a boson with I = 0, so
also, in homonuclear diatomic molecules, the consideration that in 16 O2 , Ns = 1 and Na = 0. The fact that, in the X
of the conservation of nuclear-spin symmetry, in addition 3 −
g ground state of O2 , the rotational levels of even N
to the selection rules discussed in the previous sections. values have “a” symmetry (Figure 19) implies that such
The parity of a rovibronic state indicates whether its rovi- states cannot be populated according to the generalized
bronic wave function remains invariant under inversion of Pauli principle. Consequently, all lines originating from
all space-fixed coordinates or whether it changes sign. In even N levels of the ground state of O2 are missing in
the former case, one speaks of positive parity (labeled as an electronic spectrum, and all observable transitions con-
“+”) and, in the latter, of negative parity (labeled as “−”). nect rovibronic levels of “s” rovibronic symmetry. In the X
1 +
Since g ground state of H2 , rotational levels of even J = N
values have s symmetry. H is a fermion, with I = 1/2, so
1. the dipole-moment operator has negative parity,
that Ns = 3 and Na = 1. Because the total wave function
2. wave functions in isotropic space have a well-defined
must be of “a” symmetry with respect to permutation
parity,
of the coordinates of fermions, states of rovibronic “s”
3. the parity of a product of functions corresponds to the
(“a”) symmetry only exist if their nuclear-spin symmetry
product of their parities, and
4. the integral of a function of negative parity is zero, is “a” (“s”). Consequently, transitions from odd-J rota-
tional levels of the ground state of H2 , which have “a”
the intensity of an electric-dipole transition of the form symmetry, are three times more intense than those from
(154) differs from zero only if Ψ f and Ψ i possess opposite even-J rotational levels, which have “s” symmetry. The
 Fundamentals of Electronic Spectroscopy 241

conservation of nuclear-spin symmetry implied by the sec- can then be determined from the selection rules in the same
ond factor of equation (156) means that rovibronic states way as used in the simple cases illustrated in Figure 43.
of “a” and “s” symmetry are not connected by transi- The rotational energy level diagrams presented in Figure 19
tions induced by electromagnetic radiation and can there- are helpful in predicting the overall rotational branch struc-
fore be considered as belonging to two distinct forms of ture of electronic transitions of diatomic molecules, because
homonuclear diatomic molecules, called para and ortho they provide the parity and nuclear permutation symme-
forms. One should, however, note that the product form try of the rotational levels of the most common types of
of equation (156) is an approximation, and that hyperfine electronic states.
interactions can couple the nuclear-spin motion to other
motions.
The rotational states (with parity and nuclear permutation 3.3.5 Selected Examples
symmetry) that are involved a 1 + 1 +
u ← g (parallel) The literature on the electronic spectra of diatomic mole-
and 1 u ← 1 + g (perpendicular) transitions are drawn cules is extremely rich. High-resolution spectra of elec-
schematically in the upper parts of Figure 43(a) and (b), tronic (allowed and forbidden) transitions connecting states
respectively. The allowed transitions are marked by arrows of almost all possible term symbols in all Hund’s cases
and grouped in P, Q, and R branches. Figure 43(c) and (d) have been reported. Rather than giving a comprehensive
present schematic spectra corresponding to the two types overview of all possible types of electronic transitions in
of transitions. The alternation of intensities of the lines diatomic molecules, we limit ourselves here to a few sim-
results from the fact that the spectra have been calculated ple cases, from work in our laboratory, which illustrate
for a homonuclear diatomic molecule made of atoms with the general principles in an elementary manner. Further
a nuclear spin I = 1. examples of electronic spectra of diatomic molecules can
Only ∆J = ±1 transitions are allowed in a parallel tran- be found, in this handbook, in the articles by Eikema
sition, and the rotational structure of the vibronic transition and Ubachs 2011: Precision Laser Spectroscopy in the
consists of two branches, one with ∆J = 1 (so-called R Extreme Ultraviolet, Jungen 2011a: Elements of Quan-
branch) and one with ∆J = −1 (the so-called P branch; tum Defect Theory and Western 2011: Introduction to
see Figure 43(a) and (c)). In a perpendicular transition, Modeling High-resolution Spectra. For a more complete
∆J = 0 transitions are also observable, which leads to a and systematic overview of the broad diversity of elec-
third branch (the so-called Q branch; see Figures 43(b) and
tronic spectra of diatomic molecules, we refer to the books
(d)).
by Herzberg (1989), Lefebvre-Brion and Field (2004), and
In the case of transitions between singlet states, the
Brown and Carrington (2003).
rotational structure of the bands can be approximately
Figure 44 illustrates, with the example of the C 0u + ←
described using equation (3) as:
X 0g + electronic band system of Xe2 , the Franck–Condon
principle and some of the limitations in its use that result
ν̃ = ν̃ v
v

+ B
J
(J
+ 1) − D
(J
(J
+ 1))2 from the experimental methods chosen to record electronic
− [B

J

(J

+ 1) − D

(J

(J

+ 1))2 ] (207) transitions. The electronic states of Xe2 are conveniently
described in Hund’s case (c), and the figure also gives
where J
= J

for the Q branch, J
= J

+ 1 for the R an example of the rotational structure of a 0u + ← 0g +
branch, and J
= J

− 1 for the P branch. transition, which conforms to the energy level diagram
In the case of transitions between doublet or triplet presented in Figure 43(a).
states, the rotational structure is more complicated. The Whereas the ground electronic state of Xe2 is only
spectral positions ν̃ of the rovibronic transitions are given weakly bound by van der Waals forces, the A, B, and
by (equation 3) C electronic states are the lowest members of Rydberg
series converging on the low-lying electronic states of Xe2 +
ν̃ = ν̃ v
v

+ F
(J
, . . .) − F

(J

, . . .) (208) (Figure 17) that are more strongly bound and thus have
equilibrium internuclear distances shorter than the ground
where F
and F

represent the rotational term values and state. This geometry change results in a long progression of
the “. . .” symbolize the quantum numbers necessary to des- vibrational bands corresponding to excitation of vibrational
ignate the rotational levels, which depend on Hund’s angu- levels of the C state with v
= 14–26 (Figure 44b). The
lar momentum coupling case used to describe the rotational rotational structure of the bands with the lower v
values
structure. F
and F

must be evaluated, for each state, using are strongly degraded to the high wave-number side of the
the rotational (including spin–orbit interaction) Hamilto- spectrum (Figure 44c), which also indicates a shortening of
nian presented in equation (101). The allowed transitions the interatomic distance (Bv

> Bv



).
242 Fundamentals of Electronic Spectroscopy

a+
4 s−
3 s−

s−
1Σ + 3 a+
u (0u+) 2 a+ 1Π
u (1u)

1 s− a+
2 s−
J=0 a+
s−
J=1 a+
R-branch R-branch P-branch
lines lines lines
R-branch
lines Q-branch
lines
3 a− 3 a−

1Σ +
g (0g+) 2 s+ 1Σ +
g (0g+) 2 s+

1 a− 1 a−
(a) J=0 s+ (b) J=0 s+

R(2)

R(4)
P(4)

P(2)

R(0)

R(3)
R(1)
P(3)

P(1)

(c) n0
Q(2)
Q(4)

R(2)

R(4)
R(0)
Q(6)
P(4)

R(3)
R(1)
P(2)

Q(8)
P(3)

Q(10)
Q(12)

(d) n0

Figure 43 (a) Rotational states (with parity and nuclear permutation symmetry) that are involved in a 1 + 1 +
u ← g transition. (b)
1 +
Rotational states (with parity and nuclear permutation symmetry) that are involved in a u ← g transition. (c) and (d) Schematic
1

diagram of the rotational structure of the vibrational bands of a 1 + 1 + 1 +

u ← g and u ← g transitions, respectively. The intensity
1

alternation results from the fact that intensities have been calculated for a homonuclear diatomic molecule composed of atoms with a
nuclear spin I = 1. The diagrams are also appropriate to qualitatively predict the rotational structures of 0u + ← 0g + , and 1u ← 0g +
transitions, respectively.

Because the rotational constant of the v
= 20 level of the show the intensity alternations between lines originating
C state is significantly larger than that of the ground v

= 0 from even- and odd-J

ground-state levels that are charac-
level, the P branch of the C 0u + (v
= 20) ← X 0g + (v

= teristic of the spectra of homonuclear diatomic molecules
0) band displayed in Figure 44(c) possesses a band head at (Figure 43c). The reason is that the spectrum has been
low J

values (J

= 3). The rotational structure does not recorded by measuring the ionization signal corresponding
 Fundamentals of Electronic Spectroscopy 243

77185.560
77 1
P1 + 1S0
20
C 0u+ 10
15

76 n' = 5

68045.663
68
45
3P
1 + 1S0
40 0.8
67068.047

Ion signal (arbitrary units)

35
Wave number (103 cm−1)

67
40
3P
2 + 1S0
30 35 0.6
25 30
66 20
25
15 0.4
20
10
65 15
0.2 16 ← 1
n' = 5
B 0u+ 10
64
n' = 5 0
A 1u v 14 15 16 17 18 19 20 21 22 23 24 25 26
63
76 500 76 600 76 700 76 800 76 900
(b) Wave number (cm−1 )
X 0g+
n" = 0 1S0 + 1S0
0
1 2 3 4 5
(a) Internuclear distance (Å)

4 6 7 8 9 10 11 12 13 14 15 16
1.0 P

R
1.0 31 0 1 2 3 4 5 6 7 8
0.8
0.5
Ion signal (arbitrary units)

0.0
0.6 76 713 76 713.2 76 713.4 76 713.6 76 713.8
Wave number (cm−1)

0.4

0.2

0.0 48 12 16 18 20 22 24 26 28 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44
P

R
0 4 6 8 10 12 14 16 18 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37

76 714 76 716 76 718 76 720

(c) Wave number (cm−1)

Figure 44 (a) Schematic diagram of the potential energy functions of the X 0g + , A 1u , B 0u + , and C 0u + electronic states of Xe2 .
The Franck–Condon region for excitation from the ground vibrational level of the X state is indicated by the gray area. (b) Spectrum
of the C 0u + ← X 0g + (v

= 0) transition recorded with a narrow-band pulsed VUV laser. The transitions are detected by ionizing
the levels of the C state with a pulsed UV laser and monitoring the current of 131 Xe136 Xe+ ions as a function of the wave number
of the VUV laser. The Xe2 molecules were formed in a supersonic expansion and the population of the rotational levels corresponds
to a temperature of 4 K. The vibrational bands are labeled by the vibrational quantum number of the C state. (c) Rotational structure
of the C 0u + (v
= 20) ← X 0g + (v

= 0) band. The numbers along the assignment bars corresponding to the P and R branches
designate the rotational quantum number J

of the ground state. [Adapted from Hollenstein (2003) Erzeugung und spektroskopische
Anwendungen von schmalbandiger, kohärenter, vakuum-ultravioletter Strahlung, PhD thesis, Eidgenössische Technische Hochschule
Zürich, ETH Zürich, CH-8093 Zürich, Switzerland, Diss. ETH Nr. 15237.]
244 Fundamentals of Electronic Spectroscopy

[X+(3)] 4ps 1Σ+ X 1Σ+ (0)

[X+(3)] 4pp 1Π X 1Σ+ (0)
4 3 2 1 01234
[X+(4)] 4ss 1Σ+ X 1Σ+ (0) P R
Q(1-4)
5 4 3 2 1 0 1 2 3 45 4 3 2 0 1 2 3
P R P R
1.00

0.98
Transmission signal (I /I 0 )

0.96

0.94

0.92

0.90

109 420 109 440 109 460 109 480 109 500 109 560 109 580
(a) −1
Wave number (cm )

4 3 201 5 4 3 21 [A+(2)] 3ss 1Πu X 1Σ+g (0)

b’ 1Σ+u (8) X 1Σ+g (0) R Q
2 1 4 3 2 1 0 1 2 3 45
P P R
1.00

0.95
Transmission signal (I /I 0 )

0.90

0.85

0.80

0.75

0.70

0.65
109 530 109 540 109 550 109 560 109 570 109 580
(b) −1)
Wave number (cm

Figure 45 (a) VUV absorption spectrum of CO in the region between 109 420 and 109 580 cm−1 displaying transitions from the X
1 + (v

= 0) ground state to the 4pπ 1 and 4pσ 1 + Rydberg states belonging to series converging to the v + = 3 level of the X+
2 +
ground electronic state of CO+ and to the 3sσ 1 + Rydberg state belonging to series converging to the v + = 4 level of the X+
2 +
ground electronic state of CO+ . (b) VUV absorption spectrum of N2 in the region between 109 530 and 109 580 cm−1 displaying
transitions from the X 1 +

+
g (v = 0) ground state to the 4sσ u Rydberg state belonging to series converging to the v = 2 level of
1

the A+ 2 u first excited electronic state of N2 + and to the v
= 8 level of the b
1 +

u valence state of N2 . [Adapted from Sommavilla
(2004) Photoabsorption-, Photoionisations- und Photoelektronenspektroskopie von Atomen und kleinen Molekülen im VUV-Bereich,
PhD thesis, Eidgenössische Technische Hochschule Zürich, ETH Zürich, CH-8093 Zürich, Switzerland, Diss. ETH Nr. 15688.]
 Fundamentals of Electronic Spectroscopy 245

to the 131 Xe136 Xe isotopomer. One should note that one in 1 states. The two bands centered around 109 449 and
retains the g/u labels in this case because isotopic substi- 109 481 cm−1 in the spectrum of CO and the band centered
tution does not affect the electronic structure within the around 109 542 cm−1 in the spectrum of N2 must, therefore,
Born–Oppenheimer approximation. have a 1 state as upper level.
The intensity distribution of the spectrum only partially The rotational constant of the upper vibronic state pro-
reflects the Franck–Condon factors. Indeed, the intensity vides a further important indication for the assignment,
of the ion signal can be significantly reduced by predisso- particularly when a spectrum consists of overlapping tran-
ciation of the C level. Moreover, the overall intensity dis- sitions to Rydberg states belonging to series converging
tribution can be affected if the predissociation rate depends on different ionic states. Because the rotational constants
on the degree of vibrational excitation of the C state. of Rydberg states are almost identical to the rotational
Next to information on the internuclear distances of the constants of the ionic states to which the Rydberg series
states involved in the transitions by means of the rotational converge, the determination of the rotational constant of
constants, the spectrum also contains information on the the upper level of an electronic transition can often either
potential energy functions and the electronic symmetry enable one to confirm or rule out possible assignments by
of the electronic states involved in the transition. The comparison with the rotational constants of the vibronic
same transition can also be recorded by monitoring the levels of the ion, if these are known. Such comparison, in
electronically excited Xe atom fragment that results from addition to information on the quantum defects, can be used
the predissociation of the C state (not shown), so that to assign two bands of the spectrum of CO to transitions
the electronic spectrum also contains information on the to Rydberg states with a X+ 2 + (v + = 3) CO+ ion core
dynamics of the excited state. and one to a Rydberg state with a X+ 2 + (v + = 4) CO+
A more reliable way to measure intensities of electronic ion core. Similarly, the band centered around 109 564 cm−1
transitions is by recording the absorption signal. Examples in the spectrum of N2 can be assigned to a transition to a
of VUV absorption spectra of CO and N2 are presented Rydberg state with an A+ 2 u (v + = 2) N+ 2 ion core. The
in Figure 45(a) and (b). In these spectra, the normalized much smaller rotational constant of the upper level of the
transmission signal I /I0 of the VUV radiation is displayed transition centered around 109 542 cm−1 in the spectrum of
as a function of the VUV wave number. The CO and N2 , which results in an R-branch band head at J

= 1, is
N2 gas samples are cold (T ≈ 12 K), skimmed supersonic incompatible with an assignment of the upper level to a
expansions of CO and N2 , which are crossed at right angles Rydberg state and must be assigned to the b
valence state.
by the VUV laser beam to avoid Doppler broadening. The bands observed in the VUV absorption spectra of CO
Normalization is achieved by dividing the intensity of and N2 have different linewidths and, therefore, the upper
the VUV radiation transmitted through the sample by the vibronic levels have different predissociation rates. A mea-
intensity of a reference VUV laser beam (Sommavilla et al. surement of the same transitions by resonance-enhanced
2002). two-photon ionization spectroscopy would, therefore, have
The rotational structure of the bands represents an led to different relative intensities: the bands with broad
essential element of the assignment procedure. Bands lines would have appeared less intense in these spectra
recorded from a lower level of 1 + symmetry that have compared to those with narrow lines than in the case of
P, Q, and R branches must have a 1 state as upper the absorption spectra displayed in Figure 45.
level, whereas those that do not have a Q branch are Finally, one could note that the transitions from J

= 0
likely to have a 1 state as upper level. Consequently, the and 2 levels are more intense compared to the J

= 1 and 3
bands centered around 109 562 cm−1 in the spectrum of N2 lines in the spectrum of N2 than they are in the spectrum of
(Figure 45b) and the band centered around 109 564 cm−1 CO. This difference is the manifestation of the nuclear-spin
in the spectrum of CO (Figure 45a) must have a 1 state statistical factors of 2(1) of rotational levels of even-(odd-)
as upper level, because they have a Q branch. However, J

levels of N2 (equation 206).
the absence of a Q branch does not automatically imply
that the upper level is 1 state, because P and R lines
access the components of the rotational doublets with + 3.4 Electronic Spectra of Polyatomic Molecules
electronic character, and Q lines the components with a
− electronic character. The absence of the Q branch in The general principles needed to rationalize or predict the
a 1 ←1 transition may, therefore, occasionally also structure of electronic spectra of polyatomic molecules
result from a perturbation of the − state, for instance are presented in Section 3.1, and only differ from those
by a neighboring − state. Consequently, + states can needed in studies of diatomic molecules as a result of
only be unambiguously assigned by the observation of a the larger number of vibrational degrees of freedom and
P(1) transition. Indeed, J = 0 rotational levels do not exist the different point-group symmetries. The transitions are
246 Fundamentals of Electronic Spectroscopy

classified as electronically allowed if equation (173) is Table 22 Transformation properties of electron-spin functions in
fulfilled, in which case the vibrational intensity distribution the T(2)
d spin double group.
can approximately be described by Franck–Condon factors
(equation 175) and the selection rules (176) and (177). If S 0 1/2 1 3/2 2 5/2
equation (173) is not fulfilled, electronic transitions may
S A1 E1/2 F1 G3/2 E + F2 E5/2 + G3/2
nevertheless be observed, in which case they fall into three
categories, two of which have already been discussed for
diatomic molecules in Section 3.3.2: 3. Electronically forbidden but vibronically allowed
transitions
1. Magnetic-dipole transitions and electric-quadrupole
The mechanism by which such transitions are observed
transitions
is the Herzberg–Teller intensity borrowing mechanism
This case can be treated in analogy to the discus-
mentioned in Section 3.1 in the context of electroni-
sion, in Section 3.3.2, of magnetic-dipole and electric-
cally forbidden but vibronically allowed transitions. In
quadrupole transitions in diatomic molecules
this case, the selection rule (178) applies and requires
an odd change in the number of vibrational quanta in
Example nontotally symmetric modes (equation 179). Electroni-
The à 1 A2 ← X̃ 1 A1 transition in H2 CO is electroni- cally forbidden but vibronically allowed transitions are
cally forbidden (Table 12). However, the transition is not possible in diatomic molecules, because the only
observed as a magnetic-dipole transition ((Rz ) = A2 vibrational mode is totally symmetric.
in this C2v molecule).
Example
2. Intercombination transitions
Intercombination transitions in polyatomic molecules Consider the electronically forbidden transition bet-
can also be treated following the same procedure as ween the X̃ 1 A1 vibrationless ground state and the Ã
1 A electronic state of a C
that introduced in Section 3.3.2 to treat such transitions 2 2v molecule. Excitation of a
in diatomic molecules. B1 vibration in the upper electronic state results in an
excited state of vibronic symmetry ev = A2 ⊗ B1 =
Example B2 . A transition to this state originating in the A1
state is vibronically allowed. However, the transition
We consider the à 3 F2 ← X̃ 1 A1 transition in a tetra- only carries significant intensity if the B2 vibronic
hedral molecule. The character table of the spin double state interacts with a close-lying electronic state B̃ of
group of a tetrahedral molecule is given in Table 21. electronic symmetry B2 . The intensity of the transition
(Tx,y,z ) = F2 in this group. According to Table 22, is “borrowed” from the B̃ ← X̃ transition by the
the S = 0 and S = 1 electron-spin functions trans- Herzberg–Teller effect.
form as the A1 and F1 irreducible representations,




respectively. We therefore obtain es = A1 and es =



elec ⊗ espin = F2 ⊗ F1 = A2 + E + F1 + F2 . Conse- 3.4.1 Electronically Allowed Transitions—An
quently, only the F2 component corresponds to an Example
observable intercombination transition.
The general symmetry selection rules governing elec-
Table 21 Character table of the spin double group of tetrahedral tronic transitions in polyatomic molecules have been
molecules T(2)
d .
formulated in equations (157), (158), (160)–(165), (173),
and (175)–(177). In polyatomic molecules, an electronic
Td I 8C3 6σd 6S4 3S24 R 8C23 6S34 transition can be induced by any of the three Carte-
sian components of the transition dipole moment. When
A1 1 1 1 1 1 1 1 1 an electronic transition is allowed, the relative intensi-
A2 1 1 −1 −1 1 1 1 −1 ties of the transitions to different vibrational levels of the
E 2 −1 0 0 2 2 −1 0 electronically excited state approximately correspond to
F1 3 0 −1 1 −1 3 0 1 Rx , Ry , Rz
F2 3 0 1 −1 −1 3 0 −1 x, y, z
Franck–Condon factors (equation 174), and the vibrational
structure of an electronically allowed transition contains
√ √ information on the relative equilibrium geometries of the
E1/2 2 1 0 √2 0 −2 −1 −√ 2
two electronic states connected through the transition.
E5/2 2 1 0 − 2 0 −2 −1 2
G3/2 4 −1 0 0 0 −4 1 0 An illustrative example of an electronically allowed
transition is the absorption spectrum of ammonia, which
 Fundamentals of Electronic Spectroscopy 247

n=5 n = 10 core. In the electronically excited state, the molecule has

2n0 a planar structure with D3h point-group symmetry. In this
2
point group, the excited electronic configuration and the
Absorbtion cross section (10−17 cm2)

electronic state are labeled (1a
1 )2 (2a
1 )2 (1e
)4 (1a

2 )1 (3sa
1 )1

à 1 A

2 .
1.5
230
The absorption spectrum of the à ← X̃ transition
recorded using a room-temperature sample in which only
the ground vibrational level of the X̃ state is significantly
1
220 populated is displayed in Figure 46. The spectrum con-
sists of a single progression in the out-of-plane bending
(umbrella) mode ν 2 of the à state. The origin band is
0.5
210 labeled as 000 and the members of the progression as 2n0 ,
indicating that the electronic transition originates in the
000 vibrational ground state of the X̃ state of ammonia and
0 ends in the v2 = n vibrationally excited level of the à state.
45 000 50 000 55 000
−1)
The weak band observed at lower wave numbers than the
Wave number (cm
origin band is the hot band 201 . The very long progression,
extending beyond n = 15, is characteristic of a large change
Figure 46 Absorption spectrum of the à ← X̃ transition of
in equilibrium geometry between the two electronic states
ammonia (data from Cheng et al. 2006). The origin of the
electronic transition is labeled as 000 and the dominant progression involved in the transition.
in the out-of-plane bending mode ν 2 is labeled 2n0 . The members The simplest way to understand the fact that transitions to
of this progression originate in the vibrational ground state of the both even and odd vibrational levels are observed without
X̃ state and end in the v2 = n level of the à excited state. noticeable intensity alternations between even and odd
levels is to evaluate the selection rules in the C3v point
Table 23 Character table of the D3h point group. group (see top left part of Table 16). In this group, the
electronic transition is allowed, and the umbrella mode is
D3h I 2C3 3C2 σh 2S3 3σv totally symmetric, so that the vibrational selection rule and
intensity distribution can be described by the vibrational
A
1 1 1 1 1 1 1 selection rule (177) and the Franck–Condon factors given
A
2 1 1 −1 1 1 −1 Rz
E
2 −1 0 2 −1 0 x, y
by equation (174), respectively.
A

1 1 1 1 −1 −1 −1 The vibrational intensity distribution can also be expla-
A

2 1 1 −1 −1 −1 1 z ined in the D3h point group. However, in this group, the
E

2 −1 0 −2 1 0 Rx , Ry umbrella mode ν 2 is not totally symmetric, but of a

2
symmetry. Consequently, one would predict on the basis
of equation (176) that the vibrational bands corresponding
is displayed in Figure 46. The electronic ground state of to odd values of the vibrational quantum number v2 of the
ammonia has an equilibrium structure of pyramidal C3v umbrella mode should be missing in an absorption spectrum
point-group symmetry. However, two pyramidal configu- from the ground vibrational level. The reason transitions to
rations are separated by a low barrier along the bending vibrational levels with odd values of v2 are observed is
(umbrella) mode, which leads to inversion of the molecule that they originate from the upper tunneling component of
through tunneling on the picosecond timescale and to a the ground state that has A

2 vibronic symmetry (and thus
tunneling splitting of 0.8 cm−1 . When this tunneling split- may be regarded as the first excited vibrational level of the
ting is resolved, the appropriate point group to treat the ground state). Transitions to vibrational levels with even
energy level structure is D3h , the character table of which values of v2 originate from the lower tunneling component
is given in Table 23. The vibrational wave functions are of the ground state, which has A
1 symmetry. The two
nevertheless mainly localized at the minima of the potential tunneling components are almost equally populated under
energy surfaces corresponding to a C3v geometry. In the C3v the experimental conditions used to record the spectrum
point group, the electronic configuration of ammonia in the displayed in Figure 46, so that no intensity alternations in
X̃ ground electronic state is (1a1 )2 (2a1 )2 (1e)4 (3a1 )2 . The the ν 2 progression are observed.
lowest-lying electronically allowed transition corresponds This example also served the purpose of illustrating some
to the excitation of an electron from the 3a1 orbital, which of the difficulties one encounters in interpreting electronic
is a nonbonding orbital (lone pair) of the nitrogen atom, states with equilibrium structures corresponding to different
into the diffuse 3s Rydberg orbital with a NH3 + planar ion point groups.
248 Fundamentals of Electronic Spectroscopy

3.4.2 Electronically Forbidden but Vibronically Figure 47 shows a low-resolution overview spectrum of
Allowed Transitions—An Example benzene in the region of 37 000–42 000 cm−1 , which was
first analyzed by Callomon et al. (1966). The spectrum is
Electronically forbidden transitions may gain intensity from dominated by a strong regular progression of absorption
allowed transitions through vibronic coupling mediated by bands connecting the ground vibrational level of the X̃ state
a nontotally symmetric mode (the Herzberg–Teller effect), to vibrationally excited levels of the à state. The nomen-
as discussed above. clature 1n0 610 indicates that the lower level of the transition
A prototypical example of this situation is the electron- has the quantum numbers v1 = v6 = 0, i.e., both ν 1 and
ically forbidden à 1 B2u ← X̃ 1 A1g transition of benzene ν 6 are unexcited, whereas the upper level of the transi-
(C6 H6 ). This transition is also referred to as the S1 ← S0 tion has v1 = n and v6 = 1. The origin of the band system,
transition, according to the nomenclature introduced in designated as 000 , does not carry intensity, as expected for
Section 2.3.1. The excited electronic state arises from the an electronically forbidden transition. The ν 1 and ν 6 vibra-
electronic configuration (a2u )2 (e1g )3 (e2u )1 (showing the π tional modes have A1g and E2g symmetry, respectively,
molecular orbitals only). The direct product of the irre- in both electronic states. The vibronic symmetry of the
ducible representations of the partially occupied orbitals n of the observed transition is thus e ⊗ v =
upper levels
is e1g ⊗ e2u = b1u ⊕ b2u ⊕ e1u , giving rise to the electronic b2u ⊗ a1g ⊗ e2g = e1u , which can be accessed from the
ground vibronic state through the E1u component of the
states 3 B1u , 1 B1u , 3 B2u , 1 B2u , 3 E1u , and 1 E1u . In both the
electric-dipole-moment operator (Table 13).
à 1 B2u state and the X̃ 1 A1g state, the benzene molecule has
All strong transitions in this band system end in v6 = 1
D6h point-group symmetry. The dipole-moment operator
levels, which indicates that, among all vibrational modes
transforms as A2u ⊕E1u and thus the only allowed elec-
of benzene, ν 6 is the mode primarily involved in mediating
tronic transitions originating from the ground electronic
the vibronic interaction. Below the origin of the band, the
state end in states of electronic symmetry A2u or E1u .
weak transition labeled as 601 originates from the thermally
The à 1 B2u ← X̃ 1 A1g transition in benzene is thus for-
populated v6 = 1 vibrationally excited level of the ground
bidden, while the C̃ 1 E1u ← X̃ 1 A1g transition is allowed electronic state and ends in the vibrational ground state of
(see Table 13). However, vibrational modes of symmetry the à 1 B2u state. Such a transition is a hot band and is not
b2u ⊗ e1u = e2g induce vibronic coupling between the à observed when the vibrational temperature of the molecule
and C̃ electronic states. is sufficiently low. One should note that the 610 band is
vibronically allowed, which explains why it is observed,
whereas transitions from other thermally populated excited
2.5 110610 vibrational levels of the ground state are not detected.
Absorption cross section (10−18 cm2)

2 610 3.4.3 Electronic Transitions and the Jahn–Teller

Effect
120610
1.5 The distortions of molecular structures that result from
the JT effect have a profound impact on the vibrational
1 0 structure and intensity distribution of electronic spectra.
00 130610 The reduction of molecular symmetry that follows from
JT distortions leads to the observation of dense manifolds
0.5 140610 of vibronic transitions, and the observation of vibrational
601 progressions in certain modes usually indicates that these
0 modes are JT active. In cases where the JT effect is accom-
38 000 39 000 40 000 41 000 42 000 panied by large-amplitude motions, such as pseudorotations
Wave number (cm−1) along the potential troughs as shown in Figures 30 and 31,
progressions in low-frequency modes with irregular spac-
Figure 47 Low-resolution absorption spectrum of benzene in ings are observed, the interpretation of which often requires
the 38 000–42 000 cm−1 region (data from Etzkorn et al. 1999).
The transitions labeled 1n0 610 originate in the vibrational ground extensive modeling. Rather than providing an exhaustive
state of the X̃ 1 A1g state and end in the (v1 = n, v6 = 1) treatment of the possible cases, we only present here two
vibrational states of the à 1 B2u electronically excited state. The examples, involving C5 H5 and C5 H5 + , without providing
origin of the band (marked as 000 ) does not carry intensity. The any detailed and comprehensive treatment, with the primary
vibronically allowed hot band 601 is observed below the origin goal to draw the attention to the fact that electronic spec-
band. tra of molecules subject to the JT effect are very complex
 Fundamentals of Electronic Spectroscopy 249

j = 1/2 it possesses a vibrational angular momentum || = 1, and

nj 1
j = 3/2
2 3 4 5 6 7 8 9 10 11 12 thus the à 111 state can fluoresce back to both j = 1/2
nj 1 2 3 4 5 6 7 8 9 1011 and j = 3/2 states. The complexity of the spectrum in
Figure 48 is typical of electronic transitions in molecules
D subject to the JT effect. The irregular spacings of vibronic
levels in the ground electronic state of C5 H5 and the high
density of vibronic levels at low energies are characteristic
of a strong multimode JT effect. The assignment of the
E
spectra often requires extensive theoretical modeling and
many measurements exploiting the excitation of selected
vibronic levels. The reader is referred to Applegate et al.
F (2001a,b) and to the reading list at the end of the article
for further information.
The pseudo-JT effect in the ã+ 1 E
2 state of C5 H5 + is
A
discussed in Section 2.3.6. The ã+ 1 E
2 state of C5 H5 + has
been characterized by pulsed-field-ionization zero-kinetic
energy (PFI-ZEKE) spectroscopy following resonance-
enhanced two-photon excitation through selected vibra-
0 500 1000 1500 2000 2500
tional levels of the à state of C5 H5 (Wörner and Merkt
Wave number (cm−1) 2006, Wörner and Merkt 2007, Wörner and Merkt 2009).
The pseudo-JT effect in the ã+ 2 E
1 is very strong, leading to
Figure 48 (A) Experimental emission spectrum of the
à 2 A

2 , 111 → X̃ 2 E

1 transition of C5 H5 . (D) Calculated a stabilization by about 4000 cm−1 . Moreover, the absence
spectrum of Jahn–Teller-active modes using the Jahn–Teller of significant quadratic coupling results in a vibronic struc-
parameters derived from ab initio calculations. The assignment ture that is close to the limit of a free pseudorotational
bars above the spectrum indicate the |j, nj  assignment of each motion. This limit corresponds to an unhindered large-
feature in the spectrum. (E) Simulated spectrum of Jahn–Teller amplitude motion along the minimum of the trough of
active modes using the Jahn–Teller parameters as determined
from fitting the experimental spectrum. (F) Simulated emission
the lowest potential energy surface displayed in Figure 31.
spectrum. [Reproduced from Applegate et al. (2001a).  The corresponding vibronic progressions are labeled along
American Institute of Physics, 2001.] the assignment bars at the top of Figure 49. In contrast
to the JT effect in C5 H5 , which is characterized by half-
integer vibronic angular momentum quantum numbers j
and thus particularly interesting. We refer to Section 2.3.6, (Figure 48), the pseudo-JT effect in C5 H5 + is associated
Köppel et al. 2011: Theory of the Jahn–Teller Effect, this with integer quantum numbers. The lowest progression
handbook and also to the bibliography, for more compre- (u = 0) shows the simple appearance expected for the case
hensive and exhaustive treatments of the JT effect. of free pseudorotation, i.e., vibronic level positions follow-
The JT effect in the X̃ 2 E

1 state of C5 H5 is discussed ing a quadratic dependence on their vibronic quantum num-
in Section 2.3.6. The X̃ 2 E

1 state of C5 H5 has been ber, i.e., E ∝ j 2 . At higher energies, the vibronic structure
characterized experimentally through the measurement of becomes very complicated because three vibrational modes
the laser-induced dispersed fluorescence from the first of e
2 symmetry are involved in the pseudo-JT effect. The
excited electronic state à 2 A

2 back to the ground state alternation in the intensities of the three lowest vibronic lev-
(Applegate et al. 2001a,b). The emission spectrum from els observed following excitation through different interme-
the à 111 state is shown in Figure 48. The vibrational diate states is reproduced by a simple vibronic coupling cal-
mode ν 11 is of e
2 symmetry and linearly JT active. The culation (shown as stick spectra in Figure 49) assuming that
emission spectrum is dominated by two progressions that the intensity of the forbidden ã+ ← Ã photoionization tran-
are labeled by the axes on top of the figure. The quantum sition is borrowed from the allowed ((a

2 )1 (e

1 )3 ) 1 E
1 ← Ã
number j represents the total vibronic angular momentum state through a Herzberg–Teller effect (see Wörner and
and nj represents the harmonic oscillator quantum number. Merkt 2007, Wörner and Merkt 2009, for more details).
In the electronically nondegenerate à state, the vibronic
and vibrational angular momentum quantum numbers are
3.4.4 Electronic Excitations in Complex Molecules:
identical (j = ) and, consequently, integer numbers. In the
The Exciton Model
doubly degenerate X̃ state,  is no longer a good quantum
number and each vibronic level with  ≥ 1 splits into two Large polyatomic molecules typically have a low point-
levels with j = || ± 1/2. Since the mode ν 11 is degenerate, group symmetry and, therefore, selection rules provide
250 Fundamentals of Electronic Spectroscopy

u = 0, j = 0 1 2 3 4 5

u=1
u=2
PFI-ZEKE photoelectron signal (arbitrary units)

u=3
u=4

X+ 101 X+ 132 via 00

∗ ∗
0 (a) C2

∗ via 111
∗
0

∗
∗ via 121 (b)
0

69 500 70 000 70 500 71 000

Total wave number (cm−1)

Figure 49 PFI-ZEKE photoelectron spectra of C5 H5 recorded (c)

following two-photon resonant excitation to the lower component
of the ã+ 1 E
2 state via selected vibrational levels of the à 2 A

2 Figure 50 Geometric structures of diphenylmethane possessing
state. The intermediate level is indicated on the right-hand side C2 (a), Cs (b), and C2v (c) point-group symmetries, respectively.
above the spectra. The spectra are compared to calculations Structure (a) corresponds to the geometry of the global minimum
(vertical stick spectra) of the vibronic structure including the of the ground electronic state potential energy surface. Structures
modes ν 10 , ν 11 , and ν 12 in C5 H5 + . The bands marked with an (b) and (c) correspond to saddle points of this surface (Stearns
asterisk coincide with lines of the precursor C5 H6 . [Adapted from et al. 2008). The principal axis system of structure (c) has the b
Wörner and Merkt (2007).] axis along the C2 symmetry axis, the c axis pointing out of the
plane of the page, and the a axis parallel to the line connecting
the centers of mass of the two chromophores.
much less qualitative understanding of their electronic
spectra than is the case for highly symmetric molecules. of several identical chromophores, the coupling can lead to
In large polyatomic molecules, electronic transitions are the splitting of otherwise degenerate electronic transitions.
often localized to certain groups of atoms, also called In general, the coupling can also lead to energy transfer
chromophores. This property is widely used in analyti- between different chromophores. In all these cases, the
cal chemistry to identify functional groups of molecules electronic spectrum can be qualitatively understood from
through their ultraviolet absorption spectrum (see, for the interaction of several localized excitations, which are
instance, Skoog et al. 2000). The corresponding transitions referred to as excitons (Coffman and McClure 1958).
are labeled according to the type of orbitals involved in Diphenylmethane, depicted in Figure 50, is a prototypical
the transitions, as discussed in Section 2.3.1. The alde- molecule with two nearly degenerate interacting aromatic
hyde group –CHO is an example of a chromophore chromophores (Stearns et al. 2008). The π − π∗ excitations
that possesses a weak absorption around 280 nm, corre- occur in the phenyl rings and interact with each other.
sponding to a π∗ → n promotion. Benzene rings show Diphenylmethane has a C2 equilibrium structure with the
weak absorptions close to 260 nm corresponding to π → phenyl rings at dihedral angles of approximately 60◦
π∗ excitations, as discussed in Section 3.4.2. Molecules with respect to the plane bisecting the methylene C–H
containing C=C double bonds show intense absorption bonds. Labeling the two chromophores A and B, one can
features in the region around 180 nm, just as ethylene define zero-order states |A∗ B, EA0 ∗ B and |AB ∗ , EAB0
∗
itself. corresponding to excited states with electronic excitation
In larger molecules possessing several chromophores, localized on a single chromophore. The inclusion of the
electronic excitations rarely occur independently but the coupling V between the two states leads to the exciton
chromophores are often coupled to each other. In the case states with spectral positions given by the eigenvalues of
 Fundamentals of Electronic Spectroscopy 251

the 2 × 2 matrix with diagonal elements EA0 ∗ B and EAB

0
∗ The analysis of the electronic spectra of a diphenyl-
and off-diagonal elements V methane crystal at low temperatures (Coffman and McClure
1958, McClure 1958) revealed a weak absorption band
EA0 ∗ B + EAB 0
∗ 145 cm−1 above the origin of the first absorption band,
E± =
2 which was attributed to the upper member of the exci-
 ton pair. An excited-state geometry of C2 symmetry was
(EA0 ∗ B +EAB
0
∗ ) − 4EA∗ B EAB ∗ + 4V
2 0 0 2
± (209) inferred with a very similar geometry to that of the ground
2 electronic state. In a delocalized excited system with C2
symmetry, one exciton state has a transition dipole paral-
and wave functions:
lel to the C2 axis and therefore has A symmetry, whereas
Ψ + = c1 |A∗ B+c2 |AB ∗  and Ψ − = c2 |A∗ B−c1 |AB ∗  the other has a transition dipole perpendicular to the C2
(210) axis and B symmetry. McClure 1958 thus concluded from
In the limiting case of degenerate zero-order states (EA∗ B =
0 equation (212) that the sequence of excitons was A below
0
EAB ∗ = E ), equations (209) and (210) become
0 B in diphenylmethane crystals, where A and B refer to
the symmetry of the transition dipole in the C2 point
1
group.
Ψ ± = √ |A∗ B ± |AB ∗  , E± = E 0 ± V (211)
2 The electronic transitions to these two electronic states,
also labeled S1 and S2 , were recently investigated by rota-
The magnitude and sign of the interaction between the tionally resolved laser-induced fluorescence spectroscopy
two states depend on the distance between the chro- in the unperturbed environment of a molecular jet (Stearns
mophores and the relative orientation of their transition et al. 2008). The origins of the S1 ← S0 and S2 ← S0
dipole moments. The dominant interactions are electro- transitions in (doubly deuterated) diphenylmethane-d1,2 are
static. When the separation between the chromophores is shown in Figure 51(a) and (b), respectively. The rota-
large compared to the extension of the orbitals, only the
tional analysis of the S1 ← S0 transition of diphenyl-
long-range dipole–dipole electrostatic interaction usually
methane and diphenylmethane-d1,2 shows that a-type and
needs to be considered. The electronic excitation of one
c-type Q branch transitions dominate the spectrum, which
of the chromophores induces a polarization of the orbitals
establishes the S1 state as the delocalized antisymmet-
of the other that can be described by a local transition
ric combination of the two chromophore excitations (the
dipole moment on either of the chromophores. The inter-
action of the two dipole moments is then described by the principal axes a, b, and c are defined in the caption of
dipole–dipole interaction: the figure). The origin of the S2 ← S0 transition, which
appears shifted toward higher wave numbers by +123 cm−1
µa µb
V (θ a , θ b , φ) = (2 cos θ a cos θ b +sin θ a sin θ b cos φ) in diphenylmethane and +116 cm−1 in diphenylmethane-
4π
0 R 3 d1,2 , displays b-type Q branch transitions and lacks the
(212) a-type Q branch features present in the S1 ← S0 tran-
where θ a,b are the angles between the transition dipoles of sition. This observation demonstrates that the transition
the two chromophore and the axis connecting them, φ is dipole moment giving rise to the upper excitonic state
the dihedral angle between them, and µa,b are the mag-
is parallel to the C2 axis, which further implies that the
nitudes of the two transition dipole moments. Figure 50
S2 state corresponds to the symmetric combination of the
shows three different geometric configurations of diphenyl-
two excitations. However, a complete rotational analysis
methane with point-group symmetries C2 (a), Cs (b), and
of the S2 ← S0 transition was not possible because the
C2v (c). On the potential energy surface of the ground
electronic state, structure (a) corresponds to the global vibronic coupling between the S2 and S1 states strongly
minimum that possesses two energetically equivalent enan- perturbs the spectra. This example shows that rotation-
tiomeric forms, whereas (b) and (c) are saddle points. To ally resolved electronic spectroscopy is possible in large
anticipate the manifestations of electronic excitation in this molecules, and that it can provide insight into electronic
molecule, we apply equation (212) to these structures. In excitations of complex systems. Further examples of rota-
the C2v -symmetric structure (c), the interaction between tionally resolved electronic spectra of large molecules
the transition dipole moments is maximized and the elec- are discussed in Pratt 2011a: Electronic Spectroscopy in
tronic excitation delocalized over the two rings. In the the Gas Phase and Schmitt and Meerts 2011: Rotation-
Cs -symmetric structure, the transition dipole moments are ally Resolved Electronic Spectroscopy and Automatic
perpendicular to each other and V = 0, leading to localized Assignment Techniques using Evolutionary Algorithms,
electronic excitations. this handbook.
252 Fundamentals of Electronic Spectroscopy

S1 S0 DPM-d12

Expt
Fluorescence intensity
(arbitary units)

S2 S0 DPM-d12

1 cm−1

Fluorescence intensity
(arbitary units)
Res
1 124 398 1 124 452
n (GHz)
Fluorescence intensity

Expt
(arbitary units)

Sim
1 127 866 1 127 963
n (GHz)
Res 67 % a- / 33 % c -type

−1 1
(a) nrel (GHz) (b)

Figure 51 Rotationally resolved fluorescence excitation spectra of the S1 ←S0 (a) and S2 ←S0 (b) origin bands of diphenylmethane-
d1,2 . The top panel in (a) shows the observed spectrum and the residuals (Res) from a fit of the rotational structure. The lower panel
in (a) shows the central part of the spectrum and the residuals from a fit to a- and c-type transitions on an increased scale. [Adapted
from Stearns et al. (2008).]

3.5 Nonradiative Transitions

Continuum
Electronically excited states of molecules can decay by
fluorescence to lower lying states. This process is gov-
erned by the same selection rules as photoexcitation. The |1〉
^
V
excited states can also undergo nonradiative transitions,
which can have profound effects on the intensity distri-
bution of electronic spectra. Nonradiative decay of an elec-
tronic state of an atom can only be observed above the
lowest ionization threshold and leads to the emission of an
electron. This process is termed autoionization (or preion-
ization (Herzberg 1991)) and is illustrated schematically
in Figure 52. Molecules can also decay through predis-
sociation, if the electronic state lies above at least one Figure 52 Generic illustration of the occurrence of a resonance
dissociation threshold. Autoionization and predissociation in autoionization or predissociation: an electronic level |1 is
are usually much faster than radiative decay and con- coupled to a (electronic or dissociative) continuum. The coupling
tribute to broaden absorption lines in electronic spectra is described by an interaction operator V̂ .
by reducing the lifetime of the electronically excited state.
In most molecular systems, several effects are in competi- of decay (such as internal conversion, intersystem cross-
tion. Considering an isolated level (or, more correctly, an ings, intramolecular energy redistribution, see below) are
isolated resonance) of an electronic state that can decay ignored, can be expressed as the sum of the autoion-
through a nonradiative process, its linewidth  is propor- ization a , predissociation p , and radiative r decay
tional to its inverse lifetime τ −1 and, if further sources widths:
 Fundamentals of Electronic Spectroscopy 253

electronic state. The total electronic symmetry of the ion

 = a + p + r (213)
core–electron system must be the same for the discrete
level and the continuum. An example is given by the nsσg
3.5.1 Autoionization 1
u Rydberg series converging to the A 2 u state of N2 + ,
which lies ∼9000 cm−1 above the X 2 + g ground state of
When an atom or a molecule is excited above its lowest
N2 + . The levels with n ≥ 5 are located above the ioniza-
ionization threshold, it can ionize either directly if excita-
tion threshold and can decay into the
pπu 1 u continuum
tion takes place to an ionization continuum or it can reach
associated with the ground electronic state. In general, this
an excited state that decays subsequently by autoionization
type of electronic autoionization is allowed when the two
(i.e., an autoionization resonance). In this case, the elec-
states (quasibound and continuum) are derived from con-
tron is ejected by exchanging energy with the ionic core.
figurations that differ in the occupation of at most two
Autoionization is classified according to the type of energy
orbitals, because the interaction is mediated by electrostatic
that is exchanged between the core and the electron as
interactions between electron pairs, and is proportional to
electronic, rotational, vibrational, spin–orbit, and hyperfine
1/rij . Electronic autoionization is thus an example of pro-
autoionization. The process of autoionization is discussed
cesses that cannot be explained within the Hartree–Fock
in detail by Pratt (2011b): High-resolution Valence-shell
approximation.
Photoionization, this handbook and its treatment by mul-
Rotational autoionization has been studied in greatest
tichannel quantum defect theory by Jungen (2011a): Ele-
details in the H2 molecule (Herzberg and Jungen 1972, Jun-
ments of Quantum Defect Theory, this handbook.
gen and Dill 1980). As an example, we consider the np-
Autoionization occurs because the resonance that is pop-
Rydberg states converging to the N + = 0 and N + = 2
ulated is not an eigenstate of the molecular system. Usually,
thresholds of the vibronic ground state of H2 + . The low-
a resonance can decay to different final states of the molecu-
est lying members of these Rydberg series (n ≤ 9) are
lar cation. Whereas the linewidth only provides information
best described in Hund’s case (b) and have either 1 + u
on the total decay rate, a measurement of the photoelectron
or 1 u symmetry. Their energetic positions are given by
kinetic energy distribution can provide information on the
equation (58), where the quantum defect is µσ for 1 +u lev-
product states of the ion. It is useful to define a “partial 1
els and µπ for u levels. Higher lying Rydberg states are
linewidth” for the decay of an initial state characterized by
better described in Hund’s case (d) (see Section 2.1.6). The
the electronic, vibrational, and rotational quantum numbers
autoionization width for the decay of a high Rydberg state
α, J, v to a final state of the molecular cation with the quan-
of principal quantum number n converging to the threshold
tum numbers α + , J + , v + and a photoelectron of energy
. N + = 2 into the continuum of N + = 0 is given by
Defining the interaction matrix element between the dis-
crete level |1 and the continuum to which it is coupled 2RM J (J + 1)
2
as H1,α,J,v;2,
,α+ ,J + ,v+ , the partial autoionization width can Γ n,J = 2π 3 (2J + 1)2
µπ − µσ (216)
∗
(n )
be estimated with the formula (Lefebvre-Brion and Field
where µπ and µσ are the quantum defects and J is the total
2004):
angular momentum quantum number of the autoionizing
 2 level (Herzberg and Jungen 1972, Jungen and Dill 1980).
Γ 1,α,J,v;2,
,J + ,v+ = 2π H1,α,J,v;2,
,J + ,v+  (214)
The rate of rotational autoionization is thus seen to be
In the case of an autoionizing Rydberg state with effec- related to the energy splitting between and states that
tive principal quantum number n∗ , the electronic part I originates from the nonspherical nature of the ionic core
of the matrix element H1;2 between the bound state and or, equivalently, from the interaction between the Rydberg
the continuum varies slowly with energy and the partial electron and the electric quadrupole of the ionic core.
autoionization width becomes Vibrational autoionization occurs when a Rydberg state
converging to a vibrationally excited level of the cation
2RM
Γ n,v;
,v+ = 2π I 2
v|v + 2 (215) decays into the continuum of a lower lying vibrational state.
(n∗ )3 The interaction is mediated by the nuclear kinetic energy
where RM is the Rydberg constant. Autoionization proceeds operator. The potential energy curve of a Rydberg state with
through an exchange of energy between the Rydberg elec- electronic angular momentum projection quantum number
tron and the ionic core and, therefore, its probability is Λ, Vn,Λ (R), is not strictly parallel to that of the molecular
proportional to the Rydberg electron density in the region cation V + (R), which leads to a weak R-dependence of the
of the ionic core (∝ n−3 ; see Section 2.1.6). The conceptu- quantum defect µλ (R) according to
ally simplest case is that of purely electronic autoionization.
RM
Rydberg levels converging to an electronically excited level VnΛ (R) = V + (R) − (217)
of the cation decay into the continuum of a lower lying (n − µλ (R))2
254 Fundamentals of Electronic Spectroscopy

Defining n∗ = n − µλ,(R=Re + ) and keeping only the linear 2

S1/2 ground state of 3 He+ (with nuclear spin I = 1/2)
term of a Taylor expansion of µλ (R), one can express the into the continuum of the lower lying F + = 1 level. The
linewidth for vibrational autoionization of the level n, v + hyperfine autoionization linewidth can also be estimated
into the continuum v + − 1 as (Herzberg and Jungen 1972) with equation (219) where µ3 and µ1 are the quantum
  defects in LS coupling of the 3 P1 and 1 P1 Rydberg series
2RM dµλ 2 v+ +
of He, respectively. The hyperfine interval of the 2 S1/2
Γ n,v+ −1 = 2π
φ |R̂ − Re+ |φ v −1  (218)
∗
(n ) 3 dR state of 3 He+ amounts to only 0.2888 cm−1 (Fortson et al.
1966), setting a lower limit of n ≈ 620 for the lowest level
In the harmonic approximation, the only nonzero matrix
that can decay by hyperfine autoionization. In the heavier
elements of the (R̂ − Re + ) operator are ∆v = ±1, which
rare-gas atoms, e.g., 83 Kr, 129 Xe, and 131 Xe, hyperfine
gives rise to a strong propensity rule in vibrational autoion-
autoionization rates have been predicted by calculations
ization (Berry 1966, Herzberg and Jungen 1972). In H2 , the
(Wörner et al. 2005, Paul et al. 2009).
width for ∆v = −2 autoionization is typically two orders
The discussion so far was based on the implicit assump-
of magnitude smaller than for ∆v = −1 (Lefebvre-Brion
tion of Lorentzian line shapes, which are observed when
and Field 2004).
photoexcitation populates exclusively the resonance and
Spin–orbit autoionization affects Rydberg levels lying
direct ionization is forbidden (Figure 5b of Merkt et al.
between different multiplet components of the cation. The
2011: High-resolution Photoelectron Spectroscopy, this
best known example are the rare-gas atoms Rg = Ne, Ar,
handbook). In most atomic and molecular systems, the
Kr, and Xe (see, e.g., Beutler 1935, Lu 1971, Wörner
selection rules allow both the excitation of the quasibound
et al. 2005 and also Figures 36 and 37). Rydberg levels
state and the continuum. Two pathways to the same final
converging to the 2 P1/2 level of the Rg+ ion can decay into
state exist, which results in interference phenomena and
the continuum associated with the 2 P3/2 level. Spin–orbit
in deviations of the observed line shapes from Lorentzian
autoionization also occurs in molecules, for example, in O2 .
profiles (Fano 1961). In the case of an isolated resonance
Rydberg states converging to the 2 3/2 upper spin–orbit
interacting with one continuum, the line shape is described
component of the X+ ground state of O2 + can decay into
by the Beutler–Fano formula: (Fano 1961)
the continuum associated with the 2 1/2 lower spin–orbit
component. As an example, we consider the (pπ)(nsσ) (q +
)2
3
1 and 1 1 Rydberg series converging to the X+ 2 σa = σd + σi (220)
1 +
2
state of O2 + . The lowest members of these series are
best described in Hund’s case (a) because the exchange where σd represents the cross section for direct excitation
interaction is much larger than the spin–orbit interaction in of the continuum and σi that for the excitation of the
the cation (see analogous discussion for the rare-gas atoms quasibound state. The lineshape is characterized by the
in Section 3.2.2). Therefore, their energetic position follows parameters
= (E − Er )/(Γ /2), where Er and Γ are the
the Rydberg formula (equation 58) with quantum defects energy and width of the resonance state, and q characterizes
µ3 and µ1 for the 3 1 and 1 1 levels, respectively. The the interaction between the bound state and the continuum
autoionization linewidth of the Rydberg levels converging (see Fano 1961). The limit q → ±∞ corresponds to a
to the X+ 2 3/2 substate into the continuum of the X+ Lorentzian line shape, whereas for q = 0, the resonance
2 appears as a local minimum in the cross section also called
1/2 substate is given by (Lefebvre-Brion and Field 2004)
 2 a window resonance (Figure 5 of Merkt et al. 2011: High-
2R µ3 − µ1 resolution Photoelectron Spectroscopy, this handbook).
Γ n = 2π (219)
(n∗ )3 2 The Beutler–Fano formula has been generalized to the
case of overlapping resonances by Mies (1968) and to
Consequently, spin–orbit autoionization can be considered the case of two interacting continua by Beswick and
to be a consequence of the nondegeneracy of singlet and Lefebvre (1975). In most systems, multiple overlapping
triplet levels that is caused by the exchange interaction. resonances interact with multiple continua. In such cases,
Hyperfine autoionization has been discussed only very multichannel quantum defect theory (see Jungen 2011a:
recently (Wörner et al. 2005) because it can only be Elements of Quantum Defect Theory, this handbook)
observed at very high spectral resolution and in very high is required to achieve a quantitative understanding of the
Rydberg states. It occurs when Rydberg levels converging spectral structures.
to an excited hyperfine-structure component of an ionic
fine-structure level decay into the continuum associated
with a lower-lying hyperfine component of the same fine-
3.5.2 Predissociation
structure level. The simplest case is the decay of np- Predissociation is a process by which a nominally bound
Rydberg levels converging to the F + = 0 level of the vibrational level decays into atomic or molecular fragments
 Fundamentals of Electronic Spectroscopy 255

through coupling to a dissociation continuum. Two different 3.5.3 Dynamics in Large Polyatomic Molecules
types of predissociation have been characterized: predisso-
In addition to the decay mechanisms of predissociation and
ciation by rotation and electronic predissociation.
autoionization discussed above, and which are the dominant
Predissociation by rotation occurs for levels with J > 0
decay mechanisms in small molecules, large polyatomic
when the centrifugal energy
2 J (J + 1)/2µR 2 added to the
molecules can be subject to additional types of nonradia-
potential energy curve is large enough to lead to the appear-
tive transitions. The different kinds of dynamics are often
ance of quasibound levels. Such levels lie above the dis-
described in terms of the so-called bright and dark states,
sociation threshold of their electronic state but are trapped
which can be regarded as “fictive” zero-order levels in the
behind a centrifugal barrier (see also Schinke 2011: Pho-
absence of interactions between the levels. The bright state
todissociation Dynamics of Polyatomic Molecules: Dif-
can be populated by the absorption of a photon as illus-
fuse Structures and Nonadiabatic Coupling, this hand-
trated in Figure 53 while the excitation to the dark states
book).
is forbidden. When the interaction between bright and dark
Electronic predissociation occurs when a bound vibra-
states is considered, the dark state becomes optically acces-
tional level of an electronically excited state decays by sible. The Herzberg–Teller coupling mechanism discussed
coupling to the dissociation continuum of another electronic in Section 3.4.2 may be described in these terms, the dark
state. The potential energy curves of the two electronic state being the electronically forbidden but vibronically
states do not necessarily have to cross. allowed state.
The mixing of a bound state Ψ 1,α,v,J with a state in a Different types of couplings can be distinguished, such
dissociation continuum Ψ 2,α,E,J is described by the matrix as those associated with the phenomena known as intersys-
element: tem crossing (ISC), internal conversion (IC), and internal
vibrational redistribution (IVR). In a time-dependent pic-
Hv,J ;E,J =
Ψ 1,α,v,J |V |Ψ 2,α,E,J  ture, the molecule can be thought of as being first excited
to a bright state and subsequently evolving according to the
=
φ 1 (r, R)χ v,J (R)|H |φ 2 (r, R)χ E,J (R) (221)
couplings to isoenergetic dark states. When only few states
are coupled, for instance, because the molecule is small
where r and φ are the electronic coordinates and wave or it possesses a high symmetry, periodic motions occur,
functions, respectively, R and χ are the vibrational coordi- leading to distinct structures in the absorption spectrum and
nates and wave functions, respectively, and E is the kinetic recurrence phenomena in time-domain experiments. If the
energy of the free nuclei in the continuum. The contin- bright state is coupled to a dense manifold of dark states,
uum states are taken to be energy normalized. Fano’s the-
ory of resonances shows how the discrete state amplitude
S2
is mixed into the continuum eigenfunctions (Fano 1961).
When Hv,J ;E,J varies slowly with energy, the admixture
S1 IC ISC
of the bound level into the continuum is a Lorentzian
function, with predissociation linewidth Γ E,α,v,J given
by T1

 2
Γ E,α,v,J = 2π Vv,J ;E,J  (222)
Bright state
Dark states
In diatomic molecules, if the electronic matrix element S0 Ground state
Hv,J ;E,J varies slowly with the internuclear separation R,
the matrix element can be factorized into an electronic and
a vibrational part;

Q
Hv,J ;E,J =
φ 1 (R, R)|V |φ 2 (R, R)
χ v,J (R)|χ E,J (R)
(223) Figure 53 Schematic representation of the potential energy
in which case the predissociation linewidth can be surfaces of a polyatomic molecule as a function of a vibrational
expressed as a product of an electronic and a vibrational coordinate Q of the molecule. The absorption of a photon excites
factor the molecule from the singlet electronic ground state S0 into a
bright state S2 , which subsequently decays into a set of dark
states through IC (to another singlet state, S1 ) or through ISC
Γ E,J = 2π |Ve |2
χ v,J (R)|χ E,J (R)2 (224) into a triplet state (T1 ).
256 Fundamentals of Electronic Spectroscopy

the long-time behavior mimics an irreversible decay. This Bright First Second
usually results in structureless absorption spectra (see also state tier tier

the more detailed discussion in Merkt and Quack (2011):

Molecular Quantum Mechanics and Molecular Spectra,
Molecular Symmetry, and Interaction of Matter with
Radiation, this handbook).
ISC arises from the spin–orbit coupling between elec-
tronic states of different multiplicities. Typically, it occurs
between the vibrational levels of an excited singlet state Figure 54 Schematic representation of the mechanism of inter-
that are mixed with the dense manifold of vibronic lev- nal vibrational redistribution. The level initially populated by pho-
els of a lower-lying triplet state. In diatomic molecules, toabsorption decays into a set of “first tier” states that are usually
the singlet-triplet (spin–orbit) interaction matrix element strongly coupled to the bright state. The molecule subsequently
is easily decomposed into an electronic and a vibrational decays into a denser “second tier” of states.
overlap factor. The situation is more complex in polyatomic
molecules. The coupling between two electronic states of of freedom of the molecule. IVR can also be studied by
similarly shaped potential energy surfaces decreases con- high resolution spectrosopy; when the eigenstates can be
tinuously with increasing energy separation (an effect often resolved very detailed information on the dynamics and the
refered to as the energy-gap rule). If the potential energy hierarchy of interactions can be derived (see Albert et al.
surfaces differ significantly in shape, a small number of 2011: Fundamentals of Rotation–Vibration Spectra and
“active” vibrational modes usually mediate the coupling Merkt and Quack 2011: Molecular Quantum Mechan-
and the corresponding vibrational levels are called doorway ics and Molecular Spectra, Molecular Symmetry, and
states. In this case, ISC becomes mode specific. Interaction of Matter with Radiation, this handbook).
IC is a dynamical process that conserves the total spin
of the molecule (∆S = 0). In diatomic molecules, potential ACKNOWLEDGMENTS
energy functions of the same symmetry cannot cross (a
fact refered to as the noncrossing rule). In polyatomic
We thank Dr. Urs Hollenstein (ETH Zurich) for his help in
molecules, this rule no longer applies because certain
the preparation of the figures and Drs. Martin Schäfer and
vibrational modes distort the molecule and change its point-
Julie Michaud (both ETH Zurich) for their useful comments
group symmetry. Two electronic states may thus have
on the manuscript. F. M. also thanks Dr. Pierre Pillet and
different quantum numbers in a high-symmetry region but
the Laboratoire Aimé Cotton du CNRS (Orsay, France) for
the same quantum numbers in a region of lower symmetry,
their hospitality during the summer 2009 when part of this
leading to conical intersections. A special case of conical
article was written.
intersections arises from the JT effect and is discussed in
Section 2.3.6 (see Figure 30).
IVR differs from ISC and IC in that it does not ABBREVIATIONS AND ACRONYMS
result from the coupling of different electronic states.
It occurs between near-resonant vibrational levels of the HF-SCF Hartree–Fock self-consistent field
same electronic state by rovibrational interaction (Coriolis HMO Hückel molecular-orbital
interaction, Fermi interaction, and high-order anharmonic IC internal conversion
interaction; see Albert et al. 2011: Fundamentals of Rota- ISC intersystem crossing
tion–Vibration Spectra, this handbook) and is also highly IVR internal vibrational redistribution
specific to the molecule. The interactions can be ordered JT Jahn–Teller
by their relative strength. A bright state is typically only LCAO linear combinations of atomic orbitals
strongly coupled to a relatively sparse group of dark levels, LIF laser-induced fluorescence
sometimes refered to as the first tier of states as repre- PFI-ZEKE pulsed-field-ionization zero-kinetic energy
sented in Figure 54. These levels are also called doorway REMPI resonance-enhanced multiphoton ionization
states because they are usually coupled to a second denser
set of states, known as second tier. In a time-dependent
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M. Tinkham, Group Theory and Quantum Mechanics, McGraw-
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