ABCT4772 20232 A Conglin Handout 3
ABCT4772 20232 A Conglin Handout 3
1. Brief Introduction
❑ Molecular spectroscopy is the study
of the spectra obtained by analyzing
the light absorbed or emitted by
molecules. It serves as a crucial
experimental technique for
determining and identifying molecular
structures and forms the empirical
foundation for the development of
molecular orbital theory.
❑ Different energy units used in spectroscopy for different frequency region:
Microwave spectroscopy: Hz
Infrared spectroscopy: cm-1
Electronic spectroscopy: nm
❑ Photo-assisted transition between energy levels
E1 E1
E0 E0
❑ Transition energy:
E = E1 − E0 = h absorption c = = = 1 wave number
E = E0 − E1 = h emission E = h = = 2 angular frequency
❑ Molecular spectroscopy is closely associated with the internal motions of
molecules (generally not consider the nucleus and electron spin)
▪ Translational motion
Whole atom or molecule changes position in 3D space.
▪ Vibrational motion
Motion that changes the molecule shape:
stretching, bending, and rotation of bonds.
▪ Electron motion
Electrons transition between molecular orbitals.
❑ Energy levels of molecular motion
▪ Translational motion is considered continuous due to too small
energy level interval of ~10-18 eV.
➢ Dipole moment: product of the distance between the positive and negative charge
centers and the amount of electricity carried by the charge center, a vector with the
direction from the positive to the negative charge center.
➢ Polarity: non-uniform charge distribution in a covalent bond or molecule.
2. Rotational Spectroscopy of Diatomic Molecules
2.1 Rigid Rotor Model
m2 R
m1 r1 r2
m2 R
r1 =
R = r1 + r2 m1 m1 + m2
r1 = R − r2 = R − r1
m2 m1 R
m1r1 = m2r2 r2 =
m1 + m2
2
m m R 1 1 1
I = m1r1 + m2 r2 =
2 2 1 2
= R Moment of inertia
2
= + Reduced mass
m1 + m2 m1 m2
❑ Compare classical translational motion and rotational motion
▪ Translational motion: mass m, velocity v, momentum p = mv, K.E. T = mv2/2
▪ Rotational motion: moment of inertia I, angular velocity w, angular
momentum M = Iw, K.E. T = Iw2/2
m2
2.2 Rotation of Diatomic Molecules m1
R
2
1 2 1 2
2 2
1 1 1
Hˆ = − − 2
= − t + r
2
m=m1+m2 = +
2m1
1
2m2 2 m 2
m1 m2
2
− t2 t = Et t Translational motion
2 2 = t r 2m
− −
2
r = Etotal
2
2
t
2m 2
− 2r r = Er r Rotational motion
2
2
h2
EJ = J ( J + 1) =J ( J + 1) I = R2
8 R
2 2 2
2I
− 2
r = Er r
h2 2 R 2
M J = J ( J + 1) 2
4
❑ Energy level of rotational spectroscopy
2
h2 Rotational quantum
EJ = J ( J + 1) =J ( J + 1) = F ( J ) hc = BJ ( J + 1) hc
2I 8 2 R 2 number J = 0, 1, 2, …
❑ Selection rules
▪ Overall selection rule: non-zero change in dipole moment
▪ Specific selection rule: ∆𝑱 = ±𝟏
∆𝑱 = +𝟏 for absorption spectra
Pure rotation
∆𝑱 = −𝟏 for emission spectra
∆𝑱 = ±𝟏 for rovibrational spectra
Then B = 10.59 cm −1
h
I = 2 = 2.643 10−40 g cm 2
8 Bc
m1 H m35 Cl
= = 1.62668 10−24 g
m1 H + m35 Cl
I
R= = 127.5 pm
Example: Isotope effect. DCl and HCl have the same nuclear distance but different
reduced mass μ and moment of inertia I. Hence, their absorption spectral lines have
different wave numbers, with a weak companion line appearing next to the main line.
h
= 2 B( J + 1) = ( J + 1) main line
4 R c
2
h
= 2 B( J + 1) = ( J + 1) companion line
4 R c
2
h 1 1
Isotope shift: = − = ( J + 1) −
4 R c
2
= 2 B( J + 1) 1 −
2.3 Non-Rigid Rotor Model
❑ High-resolution rotational spectra of some diatomic molecules exhibit the
spectral lines that are not exactly equally spaced but in fact converge slowly.
❑ More accurate model for rotational energy levels of diatomic molecules:
EJ = F ( J )hc = [ BJ ( J + 1) − DJ 2 ( J + 1) 2 ] hc
J = 0, 1, 2, …
= 2 B( J + 1) − 4 D( J + 1) 3
8 dx 22
3.2 Energy Level of Harmonic Oscillator
(x) | (x)|2 1 Vibrational quantum
V(x) Ev = (v + )hv
2 number v = 0, 1, 2, …
v=3 E3=7hv/2 1
1 2 1 1
− x 2
n ( x) = n H n ( 2 x )e 2
2 n!
v=2 E2=5hv/2
▪ Vibrational energy levels are equally
spaced by a constant ΔE = hv.
v=1 E1=3hv/2 ▪ Wave functions are either symmetric
or asymmetric with respect to x = 0.
% transmission
2140 cm-1
1 k
Characteristic wave number: = = 2140 cm −1
2πc
Then k = 4 2c 2 = 1853 N m −1
❑ Force constant of some diatomic molecules
HF 3958 970
HCl 2886 480
HBr 2559 410
HI 2230 320
CO 2410 1853
NO 1876 1530
3.3 Anharmonic Oscillator Model
❑ Harmonic oscillator is not very precise to describe the vibrational motion of
diatomic molecules, especially for vibrational energy levels with high v values.
❑ The potential energy V = k(R-Re)2/2 is obviously irrational: it cannot increase
infinitely with the increase of R, but should increase to a certain extent then
become zero due to the molecular dissociation into individual atoms.
❑ Morse potential function is introduced for Harmonic
correction: 8 2
xv 1
0
V ( R) = De [1 − e − ( R − Re ) 2
] =( 0
) 2
h Morse
❑ Vibrational energy levels from solving
Schrödinger equation: De (dissociation energy)
V
1 1 2 hv0
Ev = (v + )h 0 − (v + ) xh 0 D e =
4x
2 2
❑ Wave number for transition
Ev − E0
= = v 0 [1 − (v + 1) x] x: anharmonic constant R
hc
❑ Selection rules
▪ Overall selection rule: non-zero change in dipole moment
For diatomic molecules, only polar ones have vibrational spectrum.
▪ Specific selection rule: ∆𝐯 = ±𝟏, ±𝟐, ±𝟑, …
∆𝐯 = ±𝟏 — fundamental band
∆𝐯 = ±𝟐, ±𝟑, … — ovetone band
❑ Transitions with v > 1 have much lower intensities.
1 k 1 k
0 = 0 =
2 2 c
k = 4 2 v0 2 = 4 2 c 2 0 2 = 516.3 N m
4. Rovibrational Spectroscopy of Diatomic Molecules
4.1 Rovibrational Energy Level
❑ When observing HCl vibrational spectrum by a high-resolution infrared
spectrometer, each band is found composed of many spectral lines. This is
because the change in vibrational energy level inevitably causes the
change in rotational energy level.
❑ The intervals between vibrational and rotational energy levels are much
different. The vibration and rotation of diatomic molecules can be treated
completely independent, so the total energy can be regarded as a simple
sum of the two energies. If anharmonic oscillator model for vibration and
rigid rotor model for rotation are employed, the total energy of rovibrational
motion can be expressed as:
1 1 2
Ev, J = (v + )hc 0 − (v + ) xhc 0 + BJ ( J + 1)hc
2 2
4.2 Selection Rule of Diatomic Molecules
▪ Overall selection rule: non-zero change in dipole moment
For diatomic molecules, only polar ones have rovibrational spectrum.
▪ Specific selection rule: ∆𝐯 = ±𝟏, ±𝟐, ±𝟑, …; ∆𝑱 = ±𝟏
❑ Based on ∆𝑱 = +𝟏 and ∆𝑱 = −𝟏, spectral lines are divided into two groups:
▪ R branch: ∆𝑱 = +𝟏 (e.g., E0, J → E1, J+1), on the right
R = (1 − 2 x) + ( B0 + B1 )( J + 1) − ( B0 − B1 )( J + 1) 2
▪ P branch: ∆𝑱 = −𝟏 (e.g., E0, J+1 → E1, J), on the left
P = (1 − 2 x) + ( B0 + B1 ) J − ( B0 − B1 ) J 2
▪ If B1 = B0, spectral lines of R and P branch are equally spaced by 2B.
▪ ∆𝑱 = 𝟎 is forbidden, and the Q branch in the middle of R and P branches
does not appear (it appears if molecules like NO have angular momentum
about its axis), with the interval between R and P branches being 4B.
▪ In fact, B1 < B0, with the increase of J, the spectral line spacing decreases
for R branch while increases for P branch.
❑ Rovibrational transition diagram of
diatomic molecules
▪ Rovibrational spectrum can be used
to analyze the structural data of
diatomic molecules, such as
equilibrium nuclear distance Re and
bond force constant k.
▪ The intensity of the component in
rovibrational spectrum is proportional
to the population of the rovibrational
energy level generated by that
component.
▪ Population of J-th energy level can be
Intensity
described by the Boltzmann
distribution.
𝑣
Example: On both sides of the center of the rovibrational absorption spectrum of 1H35Cl,
there are several spectral lines with wave numbers of 2925.78, 2906.25, 2865.09, and
2843.56 cm-1, with the overtone at 5668.0 cm-1. What information can be obtained?
Wave number of main (fundamental) band center: 2865.09 2906.25
2906.25 + 2925.78 + 2865.09 + 2843.56
v0→1 = cm −1 2843.56
4 2925.78 5668.0
= 2885.17 cm −1
Overtone band center: v0→2 = 5668.0 cm −1
Anharmonic constant and fundamental wave number:
2885.17 cm −1 = v0 (1 − 2 x) x = 1.728610-2 P branch Q支
P支 Q branch R branch
R支 ~v
Degenerate
▪ Three pairs of quantum numbers for electron orbital motion and spin motion:
= 0, S = 1; = 2, S = 0; and = 0, S = 0, with corresponding spectral term and
relative energy: 3g- (0.0 eV), 1g (0.98 eV), and 3g+ (1.63 eV).
6.2 Selection Rule
❑ The selection rule for molecules undergoing optical transitions between
different electronic energy levels depends on the transition matrix element:
( ij ) i j d
= *
❑ Selection rule
(1) ∆S = 0; ∆ = 0, 1
(2) ∆ = 0; ∆ = 0, 1
(3) For state, + + and - - are allowed while + - is forbidden.
(4) u g is allowed while u u and g g are forbidden.
6.3 Electronic Rovibrational Spectroscopy
— Fine Structure of Electronic Spectroscopy
❑ Energy level (after considering electronic state and vibrational transition)
1 1 2
E = Ee + (v + )hc 0 − (v + ) xhc 0
2 2
❑ Transition from low energy level E’ to high energy level E’’ absorbs the
photon with the wave number of
1 1 2 1 1 2
= e + [(v'+ ) 0 '− (v' + ) x ' 0 '] − [(v''+ ) 0 ''− (v'' + ) x '' 0 ''] = 00 + ( a ' v' − b ' v'2 ) − (a '' v'' − b '' v''2 )
2 2 2 2
1 1 1 1
00 = e + ( 0 '− 0 ' x ') − ( 0 ''− 0 '' x '')
2 4 2 4
a ' = 0 '− 0 ' x ' b ' = 0 ' x '
a '' = 0 ''− 0 '' x '' b '' = 0 '' x ''
❑ Molecules are usually in the vibrational ground state, so the band series from
v’’ = 0 to v’ has the maximum intensity and is called the zero band series.
6.4 Franck-Condon Principle
❑ The intensity of an electronic transition from v’’ to v’ is related to the wave
functions by 2
I ' " Ψ v ' R Ψ ν" dτ
*