Regions of the spectrum – Different regions of molecular spectra

1. Radio frequency region : 10m – 1cm wavelength. Nuclear magnetic resonance ( n.m.r)
and electron spin resonance (e.s.r) . The energy change involved is that arising from the
reversal of spin of a nucleus and of electron and is of the order 0.001 - 10 joules /mole.
( change of spin) .

The nucleus and electrons to be tiny charged particles and their spin is associated with a
tiny magnetic dipole moment. The reversal of this dipole can interact with the magnetic
field of electromagnetic radiation at the appropriate frequency and can produce an
emission or absorption spectrum.
2. Microwave region : 1cm – 100 μm wavelength. Rotational spectroscopy. Separation
between the rotational levels of molecules are of the order of hundreds of joules/mole.
( change of orientation).

A molecule such as HCl in which the hydrogen carries a permanent net positive charge
and the other a net negative charge, is said to have a permanent electric dipole moment.

If we consider the pure rotation of HCl the plus and minus charges changes periodically,
and the component dipole moment in a given direction fluctuates regularly. This
fluctuation is exactly similar in form to the fluctuating electric field of radiation. Thus
interaction can occur , energy can be absorbed or emitted and the rotation gives rise to a
spectrum.

A molecule such as HCl in which the hydrogen carries a permanent net positive charge
and the other a net negative charge, is said to have a permanent electric dipole moment.

If we consider the pure rotation of HCl the plus and minus charges changes periodically,
and the component dipole moment in a given direction fluctuates regularly. This
fluctuation is exactly similar in form to the fluctuating electric field of radiation. Thus
interaction can occur, energy can be absorbed or emitted and the rotation gives rise to a
spectrum.

All molecules having a permanent dipole moment are said to be microwave active. If
there is no permanent dipole moment in molecules, such as in the case of H 2 and Cl 2 no
interaction can take place and the molecule is microwave inactive.

3. Infra – red region: 100 μm – 1 μm wavelength. Vibrational spectroscopy. Separation

between the vibrational levels of molecules are of the order of 104 joules/mole. ( change
of configuration)

Here it is vibration of molecules which must give a dipole change. Consider the carbon
dioxide molecule, in which three molecules are arranged linearly with a small net positive
charge on the carbon and a small negative charge on the oxygens.

During the mode of vibration known as the symmetric stretch the molecule is alternately
stretched and compressed and hence dipole moment remains zero throughout the whole
of the motion and this particular vibration is thus infrared inactive. During the
antisymmetric stretch there is a periodic alteration in the dipole moment and the
vibration is thus infra-red active.

Thus interaction can occur , energy can be absorbed or emitted and the rotation gives
rise to a spectrum.

4. Visible and ultra violet regions: 1 μm – 10nm in wavelength. Separation between the
energies of valance electrons are hundreds of kilo joules per mole. (change of electron
distribution)
The excitation of a valance electron involves the moving of the electronic charges in the
molecule. The consequent change in the electric dipole give rise to a spectrum by it’s
interaction with the electric field of radiation.

5. X - ray region: 10nm -100pm wavelength. Energy changes involving the inner
electrons of an atom or a molecule which is the order of thousand kilojoules. ( change of
electron distribution)

6. γ ray region: 100 pm – 1pm wavelength. Energy changes involve the rearrangement of
nuclear particles having energies of 109 - 1011joules per gram atom. ( change of nuclear
configuration).

Introduction to Molecular Spectra

Molecular spectra is due to the interaction of molecules with electromagnetic radiation.

Since energy levels of a molecule are more complex than that of atoms molecular
spectra is different from atomic spectra. Atoms gives line spectra, where as molecules
give band spectra. Analysis of molecular spectra gives information regarding bond
strength, bond length, bond angle etc. The total energy of a molecule is

ETotal =¿ E Rotation + EVibration + E Electronic

Molecules show band spectra:

The total energy of a molecule in the excited state is the sum of the excitation energy of
the electrons in the molecule, the energy due to the vibration of the molecule and the
rotation of the molecule. The electronic energy levels are separated by energy intervals
of the order of 1eV – 10 eV. Each electronic energy level may have a number of
vibrational energy levels which are seperated by energy intervals of about 0.1eV. Each
vibrational energy level may have a number of rotational energy levels separated by
energy intervals of the order of 0.001 eV. Thus each electronic energy level in reality
consists of a large number of levels closely spaced together. The transition between
electronic energy levels each of which is a band of number of levels gives rise to band
spectra rather than line spectra.

Pure rotational spectra:

Transition between two rotational energy levels of a molecule with the emission or
absorption of a photon gives rise to rotational spectrum. Here vibrational state of the
atom and electronic configuration of the atom remains constant. Rotational energy levels
of a molecules are quite closely spaced. Energy required for pure rotational transition is E
= 10 -3 eV. The rotational spectra lie in the microwave or near infrared region. The
wavelength range is 1cm to 100 μm and frequency range is 3x10 11 Hz

Diatomic molecule as a rigid rotator:

Consider a diatomic molecule with permanent dipole moment. The two atoms are held
together by a rigid massless rod, so that distance between them remains constant. Let
m1 and m2 be the masses of atoms separated by a rigid rotator of length ‘r’. Let ‘c’
represent the centre of mass.

From the law of moments m1 r1 = m2 r2

m2
r1 = r2 ---- (1)
m1
r = r1 + r2 ---- (2)

m2 m2 m1+¿m
r = r2 + r2 = r2 ( + 1) = ( 2
¿ ) r2
m1 m1 m1

m1
r2 = r -------(3)
m1+ m2

m2
r1 = r --------(4)
m1+ m2
Moment of inertia about centre of mass I = m1 r12 + m2 r2 2 ___(5)

Substitute equations 3 and 4 in equation 5

m2 m1
I = m1 [ r ]2 + m2 [ r ]2
m1+ m2 m1+ m2

m1 m2
By simplifying the equation I = [ ] r2
m1+ m2
 m1 m2
Moment of inertia about the centre of mass I = μ r2 ( where μ= is called the
m1+ m2
reduced mass of the system.)

1
Rotational energy of a molecule E rot = I ω2 , where I is the moment of inertia and ω
2
the angular velocity.
2
L 1 L 1 L2
Since angular momentum L = I ω and ω = E rot = I 2 =
I 2 I 2 I

h
Angular momentum is conserved L = √ J (J +1) 2 π
Where J is rotational quantum number J = 0,1,2,3,4 etc
2 2
1 h h
Rotational energy E rot = J (J+1) = J(J+1) ------ (6)
2 2
4π I
2
8π I
2
h
Where 2
= B is called the rotational constant. Unit is Joules.
8π I
E rot = B J (J+1) in Joules ------ (7)
2
hC hC h
E rot = ------ (8) = J (J+1) ------ (9 )
λ λ 2
8π I
1 h
=ν= 2 J(J+1)
λ 8 π IC
h
ν = B J(J+1) per meter . where B = 2 in m-1 J = 0,1,2,3,4 -----
8 π IC
When J = 0 ν=0
when J = 1 ν = 2B
when J = 2 ν = 6B
when J = 3 ν = 12B
when J = 4 ν = 20B

This shows that rotational energy levels are not equally spaced. According to the
selection rule transition can take place for ∆ J = +1

Consider two energy levels with quantum numbers J and (J+1)

ν J = B J ( J+1) and ν J+1 = B ( J+1) (J+2)

When the transition takes place from ν J to ν J+1

∆ ν = ν J+1 - ν J = B ( J+1) (J+2) - B J ( J+1) = B(J+1)[ J+2-J].

Energy or wave number of the spectral line when the molecule move from J to J+1 is ν J to
J+1 = 2 B ( J+1)

∆ ν = 2 B ( J+1)
When J=0 ∆ ν=2B When J=3 ∆ ν=8B
When J=1 ∆ ν=4B When J=4 ∆ ν = 10 B
When J=2 ∆ ν = 6 B This shows that spectral lines are equally spaced.

Do all molecules show rotational spectra?

Rotational spectra arise from transitions between rotational energy states. Only
molecules which have electric dipole moment can absorb or emit electromagnetic
radiation (or photons) in such transitions. The emission of radiation is due to the rotation
of electrical dipole moment. In the case of molecules like HCl, HBr or CO permanent
dipole exists since the centre of gravity of positive and negative charges do not coincide.
The component of dipole moment along a fixed direction changes periodically as the
molecule rotate giving rise to rotational spectra. For molecules consisting of like atoms
say N2, H2 etc. no such dipole moment is present, and no radiation takes place due to
pure rotation. In general, non polar diatomic molecules with identical atoms and
symmetric poly-atomic molecules do not exhibit rotational spectra.

Intensity of spectral lines:

Wave number of the spectral line when the molecule move from J to J+1 is ν J to J+1 = ∆ ν
= 2 B ( J+1)
In order to find out the intensity of the above spectral line a prime requirement is a
knowledge of the relative probabilities of transition between the various energy levels.

For instance, does a molecule have more or less chance of making the transition J= 0 to J
=1 than the transition J = 1 to J = 2? According to selection rule ∆ J = ± 1. This shows
that probability of all changes with ∆ J = ± 1 is almost the same. This does not mean that
all spectral lines will be equally intense. The intrinsic probability that a single molecule in
the J=0 state to J=1 state is the same as that of a single molecule moving from J=1 state
to J=2 state.

In a normal gas there will be different numbers of molecules in each level to begin with
and therefore a different number of molecules will carry out transitions between the
various levels.

Therefore, line intensities will be directly proportional to the initial number of molecules
in each level.

The rotational energy in the lowest level is zero, since J = 0 . So if we have N 0 molecules
in this state the number of molecules in any higher state J is given by Boltzmann’s
equation

NJ −E J−[BJ ( J +1) ]
= KT = e KT where B is the rotational quantum number
N0 e

h
B= 2 in cm-1 . By taking the values of T=200K B = 2cm-1 and J =1 state
8 π IC
NJ
= e−0.019 ≈ 0.98 . This shows that there are almost as many molecules in the J=1 state
N0
at equilibrium as in the J=0 state.
−[−BhcJ ( J +1) ]
The graph between J and KT is as shown in fig. Which shows that there is rapid
e
NJ
decrease of with increasing J. The second factor which affect the population the
N0
possibility degeneracy. Degeneracy is the existence of two or more energy states which
have the same energy.
It can be seen that each energy level is (2J+1) degenerate. Although the molecular
population decreases exponentially with J values number of degenerate levels increases
− EJ
rapidly with J. Therefore population is proportional to (2J+1) KT .
e
− EJ
The graph of (2J+1) KT verses J is as shown in the fig.
e
This shows that population rises to a maximum and then diminishes.
− EJ
(2J+1) e KT
Line intensities are directly proportional to the population of the rotational levels. This
shows that transition between levels with very low or very high J values will have small
intensities.

Vibrational spectra for diatomic molecules:

Consider a diatomic molecule HCl. There is a repulsion between the positively charged
nuclei of both atoms and between their negative electron clouds. Also, there is an
attraction between the nucleus of one atom and the electrons of the other and vice
versa. The two atoms settle at a mean internuclear distance such that these forces are
just balanced and the total energy of the whole system is a minimum. At the energy
minimum internuclear distance is referred to as the equilibrium distance, or bond length.

The vibration of atoms in molecules with respect to each other has the energy level
spacing after the rotation of molecules. Transition between vibrational levels result in the
vibrational spectra. Vibrational spectroscopy falls in the Infra – red region: 100 μm – 1 μm
wavelength Separation between the vibrational levels of molecules are of the order of 104
joules/mole. Using vibrational frequencies we can find molecular structure symmetry
bond strength, inter nuclear structure. Compressing the atoms will cause the repulsive
force to rise rapidly, while pulling them apart is resisted by the attractive force . Any
attempt to distort the bond length requires an input energy of energy. The compression
and extension of a bond is like the behaviour of a spring and the model is similar to a
simple harmonic oscillator.

The restoring force is proportional to the displacement of the atom.

F ∝−x or F = -k x where x = ( r - r equ ) , F = -k ( r - r equ )

Here k is the force constant ‘r’ the inter nuclear distance and ‘r equ ’ is the inter nuclear
1
distance at the minimum energy. Potential energy E = k ( r - r equ )2 .
2
The plot of the above equation is a parabola. This model of a vibrating diatomic molecule
is called a simple harmonic oscillator model. At r = r equ indicate the lowest energy of the
system of a diatomic molecule.
Any energy in excess of the minimum energy at optimum distance r = r equ for example
E1arises because of extension or compression of the bond. If the energy of the HCl
molecule is increased to E2 the oscillation will become more vigorous – that is degree of
compression and extension will be greater but the vibrational frequency will not change.
An elastic bond like a spring has a certain intrinsic vibrational frequency , depend on the
mass of the system and the force constant but independent of the amount of distortion.

The vibrational frequency ν o =

1
2πμ √
k where μ is the reduced mass of the system of

two molecules, and k the force constant. The wave number ν =

1
2π c μ
k
√
c 1 ν 1
[c=νλ ∴ ν= and =ν= = ]
λ λ c 2π c
1
The vibrational energy E v = ( v + ) h ν o Joules.
2
v = 0, 1, 2, 3--- the vibrational quantum number and ν o the fundamental frequency.
The vibrational energy is quantised.
1
When v = 0 E v = h ν o Joules .
2
This shows that a diatomic molecule can never have zero vibrational energy, the atoms
1
can never be completely at rest relative to each other. The quantity h ν o is known as
2
zero point energy.
The prediction of zero point energy is the basic difference between the wave mechanical
and classical approaches to molecular vibrations. The selection rule for the vibrational
transition is ∆ ν = ± 1.
Consider two energy levels corresponding to vibrational quantum numbers v and v+1.
 1 1
E v = ( v+ )h ν o and E v+1 = ( v+1+ )h ν o
2 2
When the transition takes place between them, energy change
1 1
∆ E v= h ν o [ ( v+1+ ) - (v - )] and therefore ∆ E v= h ν o .
2 2
Vibrational energy levels are equally spaced.
Since the vibrational levels are equally spaced transition between any two neighbouring
states will give rise to the same energy change. Vibrational energy changes will only
give rise to an observable spectrum if the vibration can interact with radiation. That is, if
the vibration involves a change in the dipole moment of the molecule. Thus vibrational
spectra will be observable only in heteronuclear diatomic molecules since homonuclear
molecules ( for example H2 and N2 ) have no dipole moment. Vibrational spectra lie in
the infra-red region.

Vibrational-rotation spectra for diatomic molecules:

When the vibration spectra of a diatomic molecule are analysed under high resolution
each line is found to consists of large number of closely spaced components, which are
found to be due to rotational transition.
If the molecule remains in its ground state level of electronic energy and its transition
occur between different vibrational and rotational energies the resulting spectrum is
vibrational rotational spectrum.
Due to vibration of the atoms the internuclear distance change continuously so that
moment of inertia does not remain constant because moment of inertia I = μ r2
The rotational constant will be different for different vibrational state.
ETotal =¿ E Rotation + EVibration
 1
The vibrational energy E v = ( v + ) h ν owhere v is the vibrational quantum number v =
2
0, 1, 2, 3 and ν o the vibrational frequency ν o =
1
2π μ √
where k is the force constant and μ is the reduced mass.
k

The rotational energy E rot = B J (J+1) Joules, where J is the rotational quantum number
2
h
and B is rotational constant. B = 2
Joules. When the transition takes place from
8π I
quantum state (v1 , J1) to (v2 , J2) the Energy of transition is ∆ E v = E (v2, J2) – E (v1, J1)
∆ E v= E (v2,J2) – E (v1, J1)
1 1
∆ E v= {(v2 + )h ν o+ B J2 (J2+1)} - {(v1 + )h ν o+ B J1 (J1+1)}
2 2
∆ E v= (v2 - v1)h ν o+ B [ J2 (J2+1) - J1 (J1+1)]
∆ E v = (∆ v) h ν o+ B [ J2 (J2+1) - J1 (J1+1)] -------- (1)
The selection rule is ∆ ν = ± 1 , ∆ J = ± 1
When (∆ v) = + 1
∆ E v = h ν o + B[ J2 (J2+1) - J1 (J1+1)] ------- (2)

∆ E v= h ν o+ B[ J2 (J2+1)- J1 (J1+1)] ------- (2)

For ∆ J = +1, J2 = J1+1 equation 2 becomes
∆ E v = h ν o+ B[(J1+1) (J1+1+1) - J1 (J1+1)]
∆ E v = h ν o+ B[(J1+1) (J1+ 2 - J1)]
∆ E v= h ν o+ B[(J1+1) x 2]
∆ E v= h ν o+ 2B (J1+1) ------- (3)
h ν(transition) = h ν o+ 2B(J1+1) . Therefore LHS becomes
hc
h ν (transition) = ν ν
λ(transition) = hc (transition) = h o+ 2B(J1+1)
1
ν(transition) = [h ν o+ 2B(J1+1)]
hc
2
h ν o 2B h
ν(transition) = [ + (J1+1)] here B = Joule
hc hc 2
8π I
h
ν transition = [ ν o + B(J1+1)] where B= 2 /m
8 π Ic
These lines corresponding to ∆ ν = +1 and ∆ J = +1 form the R branch of the spectra
The lines corresponding to ∆ ν = + 1 and ∆ J = −1 , i.e. J 2=J 1−1 we get P branch
of the spectra . In this case ν(transition) becomes
ν (transition ) = [ ν o−¿ 2B’J1 ]
In polyatomic molecules we can also have a Q branch where ∆ J = 0, and all transitions
lie at ν transition= ν o
Thus Q branch is a single line whose frequency is same as that of vibrational
transitional frequency. In actual practise a cluster of very closely spaced lines are
observed.
The Born-Oppenheimer approximation is a fundamental concept in molecular
quantum mechanics that simplifies the treatment of complex systems, such as
molecules, by separating the motions of electrons and nuclei. It was introduced by Max
Born and J. Robert Oppenheimer in 1927.
Basic Idea:
Separation of motion: Electrons and nuclei in a molecule move at different speeds
because nuclei are much heavier than electrons. Due to this, the approximation assumes
that the nuclei move much more slowly, while the electrons adjust instantaneously to the
positions of the nuclei.
Electrons first, nuclei second: The approximation allows solving the Schrödinger
equation in two steps:
1. Electronic Schrödinger equation: First, it treats the positions of the
nuclei as fixed and solves for the behavior of the electrons.
2. Nuclear Schrödinger equation: Once the electronic wavefunction is
determined, the forces on the nuclei (due to the electronic structure) are
used to solve the nuclear motion (vibrations, rotations, translations) while
keeping the electronic wavefunction as constant.
Assumptions:
1. Nuclei are much heavier than electrons, making their motion slower.
2. Electrons adjust instantaneously to the new positions of the nuclei, as their
dynamics are much faster.
Benefits:
 Simplifies calculations: Instead of solving a complex, fully-coupled Schrödinger
equation that includes both electron and nuclear motions, the problem is broken
into more manageable parts.
 Used extensively in chemistry: This approximation underpins much of
quantum chemistry, molecular spectroscopy, and computational methods for
molecular structure determination.

Franck-Condon principle
It is a concept in molecular spectroscopy that explains the intensity of electronic
transitions in molecules, particularly during absorption or emission of light. It is based on
the Born-Oppenheimer approximation and deals with the relative positions of nuclei
before and after an electronic transition.
A diatomic molecule has rotational energy separations of 1- 10cm -1 and the vibrational
energy separations of 3000cm-1 . Since the energies of the two motions are so different ,
a diatomic molecule can execute rotations and vibrations quite independently. The
excitation of a valance electron involve the moving of electronic charges in the molecule.
The consequent change in the electric dipole gives rise to an energy change of 10 4 cm-1 .
According to Born –Oppenheimer approximation Etotal = Eelectronic + Evibration + Erotation
Which implies that electronic, vibrational, rotational energies are independent of each
other.
A change in total energy of a molecule
∆ Etotal = ∆ Eelectronic + ∆ Evibration + ∆ Erotation
The approximate order in the magnitude of these changes is
∆ E electronic ≈ ∆ E vibration x 103 ≈ ∆ E rotation x106
The vibrational changes produce a coarse structure while rotational changes produce fine
structure.
Electronic spectrum is given by all molecules since changes in the electronic distribution
in a molecule are always accompanied by a dipole change.
(Pure rotational spectra are shown only by molecules possessing a permanent electric
dipole moment and vibrational spectra requires a change of dipole. )
According to Born –Oppenheimer approximation Etotal = Eelectronic + Evibration + Erotation
Which implies that electronic, vibrational, rotational energies are independent of each
other.
Ignoring the rotational energy Etotal = Eelectronic + Evibration Joules and
E(total)=E (elec)+ E(vib)m-1 ------- (1)
1
E(total)=E (elec)+ ( v + ) ν per meter. Here v is the vibrational quantum number v =
2
0,1,2,3,4
The energy levels of this equation is shown in the fig. The lower energy levels are
distinguished by a double prime ( v ” , e ele )and upper energy levels by single prime ( v '
, e ' elec ). Spacing between the upper vibrational levels is smaller than spacing between
the lower electronic levels because the upper electronic state usually corresponds to a
weaker bond in the molecule and hence a smaller wave number.

There is no selection rule for v when a molecule undergoes an electronic transition. That
is every transition v ” to v ' has same probability. Consider the absorption spectrum from
lower electronic state e elec
Most of the molecules exist in the lower vibrational level ie v ” = 0. So the only
transitions to be observed with appreciable intensity are those with transitions v ” = 0 to
v ' = 1,2,3,4 .
These transitions are conventionally represented as ( v ” , v ' ¿ . So that transitions with
appreciable intensity are those (0, 0), (1,0), (2,0) etc. Such set of transitions are called a
band because under low resolution each line in the set appears broad and diffuse.
Such a set of transition is also called a v ' progression, since the value of v ' increases by
unity for each line in the set.
Also, the lines in a band crowd together more closely at high frequencies. This is a direct
consequence of the anharmonicity of the upper state vibration which causes the excited
vibrational levels to converge.
Molecules have many excited electronic energy levels, so that the absorption spectrum
of a diatomic molecule will be more complicated than the above fig because ground state
can go to many excited electronic energy levels.
Although there is no selection rule for v when a molecule undergo an electronic
transition, that is every transition v ” to v ' has same probability the vibrational lines in a
progression are not all observed to be of the same intensity.
In some spectra the (0,0) transitions is the strongest, in others the intensity increases to
a maximum at some value of v ' while in others only a few vibrational lines with higher
values are seen.
All these different types of spectra can be explained in terms of the Frank - Condon
principle which states that an electronic transition takes place so rapidly that a vibrating
molecule does not change it’s internuclear distance appreciably during the transition.
Intensity of vibrational –electronic spectra: Frank – Condon principle
The energy of a diatomic molecule varies with the internuclear distance.
The Morse curve (figure below) represents the energy where one atom is fixed on the r =0
axis and the other is allowed to oscillate with respect to r equilbrium between the limits of the
curve. According to classical theory the oscillating atom would spent most of the time on
the curve at the turning point of it’s motion. According to quantum theory this happens
only for higher values of vibrational quantum number where as for v=0 the atom is most
likely to be found at the center of it’s motion, that is at requilbrium .

For v = 1,2,3 the most probable positions steadily approach the extremities until for
higher values of v the quantum and classical picture merge.
If a diatomic molecule undergoes a transition into an upper electronic state in which the
excited molecule is stable then the upper state can be represented by the similar Morse
curve.

Case 1. The upper electronic state has the same internuclear distance as the lower
electronic state. The Frank -Condon principle suggest that a transition occurs vertically
on this diagram since the internuclear distance does not change. For a molecule in the
energy level e “ = 0 and v ” =0 the most probable transition is indicated by the vertical
line. Thus the strongest spectral line in the line v ' progression is (0,0). This is observed
in Oxygen molecule.
Case 2
Here the excited electronic state has a slightly smaller internuclear distance than the
ground state. A vertical transition from the level v ” = 0 more likely to happen in to the
upper vibrational level level v ' = 2, transition to lower and higher v ' states being less
likely. The upper state most probably reached will be depend on the difference between
equilibrium separations in the upper and lower state. In the case of CO this type of band
system is observed.

Case 3. When the upper state separation is drawn as considerably greater than that of
the lower state , then the vibrational level to which a transition takes place has a higher
v ” value. Further the transition can occur to a state where the excited molecule has
energy in excess of it’s own dissociation energy. From such states the molecule will
dissociate without any vibration and the atoms may take up any kinetic energy. The
translational energy is not quantized and a continuum results.
Summary:
The Franck-Condon principle is crucial for understanding why certain electronic
transitions are more likely than others based on vibrational state overlap and explains
why vibrational excitation often accompanies electronic excitation.
1. Nuclear positions remain unchanged during an electronic transition:
Since electronic transitions happen very quickly compared to the movement of
nuclei, the nuclei do not have time to move during the transition. This implies that
the transition is "vertical" in a potential energy diagram, meaning the nuclear
configuration stays the same when the molecule jumps between electronic states.
2. Overlap of vibrational wavefunctions: The probability of a transition is
governed by how much the vibrational wavefunctions of the initial and final
electronic states overlap. The greater the overlap, the more intense the transition.
3. Vibrational Excitation: After an electronic transition, the molecule often ends up
in a vibrationally excited state of the new electronic energy level because the
nuclear positions are the same, but the potential energy surface is different.
Diagram Explanation:
In a potential energy diagram, where energy is plotted against the internuclear distance:
 The electronic transition happens vertically, reflecting no nuclear movement
during the transition.
 The most probable transitions occur between vibrational states whose
wavefunctions have the greatest overlap.
Applications:
 Spectroscopy: Helps explain the vibrational structure seen in electronic spectra
(such as absorption or fluorescence spectra).
 Photochemistry: Describes how molecules absorb and emit light and provides
insight into molecular behavior after excitation.