Lecture 30

Molecular Electronic
Spectroscopy II

Study Goal of This Lecture

• Franck-Condon overlap and Franck-Condon principle

• Elementary photophysical process

30.1 Franck-Condon Overlap and Franck-Condon Prin-

ciple

30.1.1 Franck-Condon Overlap

In the previous lecture, the selection rules of molecular electronic spectroscopy

is presented. It depends on the transition dipole:
Z Z Z
µ12 ' Ψ1 (R = Re )µˆe Ψ2 (R = Re )dτe Ψν=0 Ψν dτvib × Ψ∗s Ψ0s dτs
∗ ∗
0

Z (30.1)
= µ0,12 × Ψ∗ν=0 Ψν 0 dτvib × δs,s0 .

From above, we observe that the selection rules of molecular electronic transition
are:

1. Non zero electronic transition dipole.

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 2. Overlap of vibrational wavefunctions between ground and excited electronic
PES.

3. Spin function cannot change.

In this lecture, the first two rules will be well focused on. Let’s look at the second
point first. The overlap is called the “Franck-Condon overlap integral”
Z
Sν,ν 0 = Ψν Ψν 0 τvib . (30.2)

What does this mean and what this tells us about the “state” after excitation? It is
explained by the following diagram:

Figure 30.1: Potential energy surface of two electronic states and the first few vibra-
tional states in electronic excited state.

In this case, the largest overlap S0,ν occurs at ν = 0 → ν 0 = 2.

30.1.2 Franck-Condon Principle

What is the physical meaning of this? Recall that in our treatment of excitation
due to electromagnetic field, after excitation the new state can be written as a

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superposition
X
bk Ψ0k
 
|Ψf i = (30.3)
k

where the coefficient are proportional to the transtion dipole µf →k . Therefore, after
excitation the wavefunction of the excited state:
X X
Ψ1 Ψν=0 −→ µ0,12 S0,ν 0 =k Ψ2 Ψν 0 = Ψ2 S0,ν 0 =k Ψν 0 .
k k

What is the vibrational part after excitation? Recall the rule for basis transform in
QM:

Any wavefunction |ψi can be written as a superposition on a “basis” {φi },

X
|ψi = C n φ φn (30.4)
n

where Z
Cn = hφn |ψi = φ∗n ψdτ. (30.5)

S0,v0 =k Ψ0v is exactly Ψν=0 written in a different basis (vibrational states of

P
k
the excited electronic state.) Therefore, in the excitation, the electronic wavefunction
changes from Ψ1 → Ψ2 , but the nuclear wavefunction stays the same, because nuclei
move much slower than electrons and have no time to respond to electronic transition.
This is called the Franck-Condon principle. The principle is more general than just
for optical transitions. It is everywhere in physical chemistry from excitation energy
transfer(EET) to electron transfer(ET). I am making a living one of it.

In an electronic process, nuclei have no time to move, so the nuclear wave-

function stays the same!

The electronic contribution is also important:

Z
µ0,12 = Ψ∗1 (R = Re )µ̂e Ψ2 (R = Re )dτe , (30.6)

electronic transition dipole at the molecular equilibrium structure between two many
electron states.
Note that both Ψ1 and Ψ2 are many-electron wavefunctions! From the inspection
of the expression we inmediately know:

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1. (Optional)For linear molucule: µ̂e has ẑ character, i.e. is an odd function
in z and both cos θ character. Recall that for such molecules with cylidrical
symmetry, we can define molecular terms.
For many electrons:

• Orbital angular momentum: ML = m1 + m2 + · · ·

• Axial quantum number: Λ = |ML | = 0, 1, 2, 3, · · ·
• Symbol: 1 → Σ, 2 → Π, 3 → ∆, 4 → Φ,· · ·
• Axial spin quantum number: Σ = S, S − 1, · · · , −S
• Total angular momentum: Ω = |Λ + Σ|
• Molecular term symbol: 2S+1 Λ
Ω

the selection can be derived as:

∆Λ = 0, ±1, ∆S = ∆Σ = 0, ∆Ω = 0, ±1

Figure 30.2: Figure of molecular term symbol.

2. State symmetry selection rule I:

~ axis, then + ↔ +, − ↔ −
For molecules with a symmetry plane containing µ
transition are allowed, but + ↔ − are not due to µ̂ is symmetry.

3. State symmetry selection rule II:

For molecules has an inversion center, µ̂ is odd(u), then g ↔ u are allowed,
but u ↔ u, g ↔ g are not.
For instance: absorption of polyenes, such as β-carotene

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 Figure 30.3: Transition rule of beta-carotene.

4. Orbital transition rules:

Note that within the Hartree-Fock approximation, we can write Ψ1 , Ψ2 as prod-
ucts of molecular orbitals, then the transition rule apply to MO level. Elec-
tronic transition can be considered as promoting an electron from an occupied
MO to an unoccupied MO(virtual orbital).

Figure 30.4: Left one is the HF groundstate, and the right one is the excited state.
Note that the transition energy in left one is under the “frozen orbital” approxima-
tion.

Under this MO picture, we find two selection rules:

• φ1 and φ2 must have different parity.

• Note that between µ̂ is linear in electron coordinate. i.e. combination of

single electron operators, it can only change one electron at a time, so all
changes involving more than one electron are forbidden in the HF level.

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 These transition rules allow us to understand molecular electron(UV/Vis) spec-
trum and assign transitions to peaks. Nevertheless, what is the UV/Vis experiments
tell us?

30.2 Absorption Pattern

Recall, absorption rate from |1i → |2i is

dN2
= Bρν (ν12 )N1 , (30.7)
dt

therefore, absorption from the ground state tells us how many molecules are in the
state. A method to measure concentration. This is Beer-Lambert Law:

dI
= −κ · c · dx (30.8)
I
I0
→ log = A =  · c · L, (30.9)
I
κ, , c and L are Napierian molar absorption coefficient, molar extinction coefficient,
concentration and path length, respectively.

30.2.1 Shape of absorption “bond” reveals elementary photophys-

ical process.

So far we have considered absorption, stimulated emission and spontaneous emis-

sion of molecular in ideal conditions. i.e. gas phase. Now we consider a displaced
harmonic oscillator model:

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 Figure 30.5: Displaced harmonic oscillator model

in this case, the Franck-Condon overlap is

Z 2 sm
 Ψ∗ν 00 =0 Ψν 0 =m dτ  = e−s (30.10)
 
m!
µω0 2
where s = 2~ d and it is called Huang-Rhys factor, represent the coupling strength
between nuclear and electronic degrees of freedom. Different s affect the absorption
pattern.

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 Figure 30.6: Huang-Rhys factor and absorption pattern.

When the upperstate can “relax”, the linewidth contains information about the
life time.

Figure 30.7: Absorption lineshpae under different phase.

The bandwidth/linewidth tells the lifetime of the excited states and can reveal
information about many elementary photophysical process.

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30.2.2 Stoke’s Shift

There is one famous phenomena called Stokd’s shift, it worths a notice. When
we plot the absorption spectrum and the emission spectrum together in the same
graph, we will find that the two highest peaks do not coincide. The shift between it
is called Stoke’s shift
It is stemed from that the most stable geometry of the molecule in the ground
state and excited state are generally not the same . So, when we excite a molecule
from electronic ground state to the electronic excited state, this excited state have
the higher energy than it is in equilibrium(The most stable geometry.) And while a
molecule are going to radiate its excess energy and transfer to the electronic ground
state from electronic excited state, the energy of this electronic ground state will
also have higher energy than it is in equilibrium. Thus, the absorption enrgy will be
larger than the emission energy in general.

Figure 30.8: Stoke’s shift

30.3 Jablonski Diagram

After the molecule be excited to the excited state, there are lots of processes can
happen. It is useful to describe those process via the Jablonski diagram.

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 Figure 30.9: Jablonski diagram.

1. Excitation (∼ 10−15 s)
A state absorbs the energy and transfer to a higher energy state.

2. Vibrational relaxation (∼ 10−14 − 10−11 s)

The system loss its energy and transfer to a lower energy state via vibrational
motions.

3. Internal conversion (∼ 10−14 − 10−11 s)

Nonradiative transition between two state with the same multiplicity.

4. Fluorescence (∼ 10−9 − 10−7 s)

Radiative transition between two states with the same multiplicity.

5. Intersystem crossing
Nonradiative transition between two states with the different multiplicity.

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 6. Phosphorescence (∼ 10−3 − 10−2 s)
Radiative transition between two states with different multiplicity.

7. Nonradiative relaxation
The system loss its energy and transfer from high energy state to low energy
state via nonradiative processes.(Not necessary via vibrational motion, other
processes such as dipole-dipole interaction or Coumlomb interaction can cause
relaxations.)

The approximated life time of those processes are given, one should have a vague
memory about it. There still other processes can occur after an system was ex-
cited such as excitation energy transfer, · · · . Those contents are beyond this course
but every student has already equipped enough abilities to study those contents by
themselevs.

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