27/11/2024

CHEM 260:
Physical Chemistry II

Kinetics 10 – Photochemistry

Dr Matthew Dyer
[email protected]
Office: Surface Science Research Centre (SSRC)
Access to SSRC via telephone in entrance porch
1

Lecture 9 - reminder

1. Cl2 → 2 Cl·
2. 2. Cl· + H2 → HCl + H·
H2
C
H3C C CH2
H2C CH2 H 3. H· + Cl2 → HCl + Cl·
4. Cl· + Cl· → Cl2

1ൗ
d[P] 𝑘2 [E]0 d[P] 𝑘2 𝑘1 [C]2 𝑘1 2
1ൗ
= = 𝑟𝑎𝑡𝑒 = 𝑘2 Cl2 2 H2
dt K dt 𝑘−1 C + 𝑘2 𝑘4
1+ M
[S]0

1
 27/11/2024

Lecture 10 - outcomes
By the end of Lecture 10 we aim to:

1. Studied Jablonski diagrams

2. Discussed rates of excitation, vibrational relaxation, excited state decay
3. Understood Quantum Yield measurements
1. Understood fluorescence and phosphorescence - Stern-Volmer Plots
2. Introduced photochemical reactions

Additional Resources
1. “Physical Chemistry”, Atkins, Oxford University Press, 11th Ed. p762-
2. Elements of Physical Chemistry: p. 479-482, 487-493
3. https://chem.libretexts.org/Textbook_Maps/Physical_and_Theoretical_Chemistry_
Textbook_Maps/Supplemental_Modules_(Physical_and_Theoretical_Chemistry)/S
pectroscopy/Electronic_Spectroscopy/Jablonski_diagram

Electronic Excitations
➢Assume we start with a molecule in a ground state LUMO
where all the electrons are paired in molecular S0
orbitals. This is the singlet state, S0. HOMO

➢Selection rules state that if we excite an electron

LUMO
with light, we cannot change its spin. We still have S1 hν
the same number of electrons with up and down HOMO
spin. We excite to another singlet state, S1.

➢There are also accessible excited states with LUMO

different numbers of up and down electrons, e.g. T1

the triplet state T1. HOMO

2
 27/11/2024

Photochemistry
➢Covered in detail in Semester 2 section, here
Vibrational Transition (~0.1 eV)
we explore the kinetics of photochemical
principles

➢Jablonski Diagram:
➢Simplified portrayal of the relative positions
of the electronic energy levels and
associated vibrational states
➢The states are arranged vertically by energy
➢Horizontal separation of different states
Electronic Excitation (~1 eV)
bears no resemblance to nuclear separation S0 → S1

1. Rate of Excitation
Transition rate (W12) from S0 → S1
𝑑 S0 𝑑𝑛1
− =− = W12 = B()n1 kexc
𝑑𝑡 𝑑𝑡

B = Einstein coefficient of stimulated

absorption
() = photon density at wavelength ()
n1 = population (concentration) of ground
state (S0)

→ first order kinetics!

Note: The rate constant for excitation depends on light intensity
6

3
 27/11/2024

Franck-Condon principle
• Electronic transitions occur much faster than nuclei
can respond
– Nuclei are much larger than electrons

• Vertical transitions – an electronic transition

without a change in nuclear geometry

• The excited state energy profile is typically offset

versus the ground state
– Excite into a higher vibrational level
Get vibrational relaxation to the lowest vibrational state of the excited state
7

Vibrational relaxation
➢ Non-radiative relaxation of vibrations
- no photon emission, energy lost as heat to
surroundings

➢ Vibrational relaxation through interactions with

solvents, other molecules

➢ Can occur within S1, T and S0 S1* krel

S1
➢ Very fast
kexc
krel (ps) >> kIC, kfl, kISC (ns)

→ often can ignore S1* for kinetics S0

8

4
 27/11/2024

Intersystem crossing
Simplified
• Transfer between spin states can occur – S1 kISC
through spin-orbit coupling
T1
kexc
• Recall the definition of singlet and triplet
states
S0
S1* krel
• The rate constant for intersystem crossing kISC
S1 T 1* k
is kISC rel'
kexc T1
• Relaxation to lowest vibrational level will
rapidly occur post ISC (not usually shown)
S0

Decay of S1 state
• Fluorescence – photon emission
S1 → S0 + hν + (heat)

• kfl typically ~1 x 109 s−1 (τ ~ ns)

– Spin allowed process
S1 kISC
• Or Internal conversion
– Relaxation to lower energy excited state T1
kIC
without the emission of a photon kex kfl
c
– Thermal relaxation (heat)
S0

10

5
 27/11/2024

Decay of S1 state
Kinetics in the absence of a quencher - parallel reactions for 1st order steps (video 15)

S1 kISC

T1
kIC
kfl

S0

Yields readily calculable from rate constants

And kinetics governed by sum of the rate constants
11

Decay of S1 state
Kinetics in the absence of a quencher – 1st order

• φT1 = kISC / (kIC + kISC + kfl) S1 kISC

(probability of ending up in T1, important for photochemistry)
T1
kIC
kfl
• φ fl = kfl / (kIC + kISC + kfl)
(probability of emitting fluorescence photon)
S0
- Observed Half-Lifetime of S1:
t1/2 = ln(2) / (kIC + kISC + kfl) Remember that even
if Φfl = 1 the energy
- Observed lifetime for fluorescence yield is lower
τobs = 1 / (kIC + kISC + kfl) hνfl < hνexc
12

6
 27/11/2024

Quantum yield
• φ fl = kfl / (kIC + kISC + kfl) S1 kISC

➢ This is the quantum yield kIC

T1
number of events kfl
Φ=
number of photons absorbed

S0
➢ How can we measure kfl?
τobs = 1 / (kIC + kISC + kfl) Emission
spectroscopy
𝑘𝑓𝑙 1 ϕ𝑓𝑙
Pulsed laser
τobs = × =
𝑘𝐼𝐶 +𝑘𝐼𝑆𝐶 +𝑘𝑓𝑙 𝑘𝑓𝑙 𝑘𝑓𝑙
spectroscopy ϕ𝑓𝑙
Then 𝑘𝑓𝑙 =
𝜏𝑜𝑏𝑠

13

Worked example
Q. The fluorescence quantum yield of tryptophan in water at 298 K is φfl = 0.20
and the measured half-life is 1.8 ns, calculate kfl
Hint: t1/2 = In(2)/kobs and τobs = 1/kobs so τobs = t1/2/In(2)

14

7
 27/11/2024

15

Fluorescence Quenching
• Molecule Q can interact with S1
• Deactivates excited state
• New 2nd order decay channel (bimolecular)
rate of quenching = kQ[Q][S1]

• Treat kQ[Q] as pseudo first-order rate constant

since [Q] is in excess over S1

fl [Q] = kfl / (kIC + kISC + kfl + kQ[Q])

16

8
 27/11/2024

Stern-Volmer kinetics
Without quencher
fl [Q] = kfl / (kIC + kISC + kfl + kQ[Q])
𝑘𝑓𝑙
ϕ0 𝑘 + 𝑘𝐼𝑆𝐶 + 𝑘𝑓𝑙
= 𝐼𝐶 ൚ 𝑘𝑓𝑙
ϕQ
𝑘𝐼𝐶 + 𝑘𝐼𝑆𝐶 + 𝑘𝑓𝑙 + 𝑘𝑄 [𝑄]
With quencher

ϕ0 𝑘𝐼𝐶 + 𝑘𝐼𝑆𝐶 + 𝑘𝑓𝑙 + 𝑘𝑄 𝑄 𝑘0 + 𝑘𝑄 𝑄

= =
ϕQ 𝑘𝐼𝐶 + 𝑘𝐼𝑆𝐶 + 𝑘𝑓𝑙 𝑘0

ϕ0 𝑘𝑄 [𝑄]
=1+ Overall rate constant
ϕQ 𝑘0
Without quencher
ϕ0
= 1 + τ0kQ[Q]
ϕQ

Where τ0 is the measured lifetime in the absence of a quencher

17

Phosphorescence
➢ Phosphorescence → photon emission

➢ T1: triplet state → decay to S0

➢ spin-forbidden
➢ slow (typ. ms to s)
➢ T1 usually lasts longer than S1

➢ Typically kph ~ 101 s-1 (very slow)

➢ Note: hνph < hνfl < hνexc

18

9
 27/11/2024

Photochemistry – An example
Photochemical Reduction
of CO2

We want to avoid emission

and use the excited state to
drive a chemical reaction

CO2 + 2e- + 2H+ → CO + H2O

Annual Review of Physical Chemistry 2012 63:1, 541-569

19

Photochemical reactions
• Examples include our well visited H2 + Cl2
reaction, O3 kinetics
• Reaction types:
– dissociation (from S1 or T1)
– reaction with M (more likely with the longer
lived T state)
• Yield of (primary) photoproduct for a reaction
between M and T1:
φphotochem = φT1 × φM
φphotochem = φT1 × kM[M]/(kM[M]+kph)
Remember that sometimes the photoproduct starts a chain reaction then Φ > 1 can occur
(e.g. Cl2 → 2Cl.)
20

10
 27/11/2024

Lecture 10 – Photochemistry
• Rate of Excitation
• kexc depends on light intensity
• Vibrational Relaxation
• Dissipation of energy as heat
• Very fast, can usually ignore for kinetics
• Non-radiative Decay
• Internal conversion (S1 → S0)
• Intersystem crossing (S1 → T1)
• Radiative Decay
• Fluorescence (S1 → S0)
• Phosphorescence (T1 → S0)
• Photochemistry
21

Lecture 10 - outcomes
By the end of Lecture 10 we aim to:

1. Studied Jablonski diagrams

2. Discussed rates of excitation, vibrational relaxation, excited state decay
3. Understood Quantum Yield measurements
1. Understood fluorescence and phosphorescence - Stern-Volmer Plots
2. Introduced photochemical reactions

Additional Resources
1. “Physical Chemistry”, Atkins, Oxford University Press, 11th Ed. p762-
2. Elements of Physical Chemistry: p. 479-482, 487-493
3. https://chem.libretexts.org/Textbook_Maps/Physical_and_Theoretical_Chemistry_
Textbook_Maps/Supplemental_Modules_(Physical_and_Theoretical_Chemistry)/S
pectroscopy/Electronic_Spectroscopy/Jablonski_diagram

22

11
 27/11/2024

Course summary
• To reinforce the basic ideas on factors affecting the rates of chemical
reactions and quantify the kinetics
• To make students familiar with the basic ideas of photochemistry
1. Introduction to rates, rate laws, reaction order
2. The Arrhenius equation and catalysis, elementary and multi-step reactions
3. Simple Collision Theory and its limitations
4. Integrated rate equations and their use, half-life, lifetimes
5. Complex reactions, consecutive processes and the RDS
6. Parallel kinetics, relaxation towards equilibrium.
7. Approximations: pre-equilibrium, steady state. Reactions in dilute solutions
8. Application of the steady state approximation: enzyme kinetics, L-H kinetics, chain reactions
9. Photochemistry

23

12