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There are 03 types of photochemical processes:

1. primary: produced product from direct excitement of reactent on absorption of lignt .
2. Secondry : molecule absorb light and become sensitized , react with unstable/stable species (intermdiate) from excited state.
This indirectly exposure of light toward molecule.
3.photophysical: it is post exciteded state. when molecule become de active and become in ground state and formed post excitex
photo product , then process is called photophysical process.

Kinetics of photochemical reactions

•  Primary photochemical process:

products are formed directly from the excited
state of a reactant.

•  Secondary photochemical process:

intermediates are formed directly from the
excited state of a reactant.

•  Photophysical processes compete with the

formation of photochemical products via
deactivating the excited state

Distinction between singlet and triplet

states

oposite spin same spin directions

directions

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Jablonski’s Diagram

importent

Time Scales

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Examples of Photochemical Processes

1. occur in Uv region
2. occur in visible reg.
3. occur in vis & infra red reg.
Uv region
dissociation
4.
is two type
Uv region
addition is two types
at low band
and at high band

5. Uv region
6.

Common Photophysical Processes

a. absorption and excite based processes

( singlet state to light and ground state)

(M is any third body)

b.

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Primary Quantum Yield

si
•  The primary quantum yield, φ, the number of
photophysical or photochemical events that lead to
primary products divided by the number of photons
absorbed by the molecules in the same interval, or
the radiation-induced primary events divided by the
rate of photo absorption:

number of events (photochemical or photophsyical process)

ϕ =
number of photons absorbed
v (rate of the process)
=
I abs (int ensity of light absorbed )

Primary Quantum Yield (mathemetically expression of primary yield)

•  The sum of primary quantum yields for all

photophysical and photochemical events must be
equal to 1:
vi
∑ϕi = ∑ =1
i i I abs
•  From the above relationship, the primary quantum
yield may be determined directly from the
experimental rates of ALL photophysical and
photochemical processes that deactivate the excited
state: vi
ϕi =
∑v i

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Decay Mechanism of Excited Singlet State

•  Absorption: S + hvi → S* vabs = Iabs

•  Fluorescence: S* → S + hvi vf = kf[S*]

•  Internal conversion: S* → S vIC = kIC[S*]

•  Intersystem crossing: S → T* vISC = kISC[S*]

S* is an excited singlet state, and T* is an excited triplet state.

The rate of decay:

d[S*]
= - k f [S*] - k IC [S*] - k ISC [S*]
dt
When the incident light is turn off, the excited state decays exponentially:
−t/τ 0 1
[S*]t = [S*]0 e with
τ0 =
k f + k IC + k ISC

Fluorescence Quatum Yield

•  If the incident light intensity is high and the absorbance of the

sample is low, we may invoke the steady-state approximation
for [S*]:
I abs - k f [S*] - k IC [S*] - k ISC [S*] = 0

Consequently,
I abs = k f [S*] + k IC [S*] + k ISC [S*]

The expression for the quantum yield of fluorescence becomes:

vf kf
φ f ,0 = =
I abs k f + k IC + k ISC

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Quenching
•  The presence of a quencher, Q, opens an additional channel
for deactivation of S*:
S* + Q → S + Q vQ = kQ[Q][S*]

Now the steady-state approximation for [S*] gives:

I abs - k f [S*] - k IC [S*] - k ISC [S*] − kQ [Q][S*] = 0

The fluorescence quantum yield in the presence of quencher

becomes:
kf
φf =
k f + k IC + k ISC + kQ [Q]

Quenching & Stern-Volmer Plot

•  The ratio of Φf,0/ Φf is then given by

ϕ f ,0
= 1 + τ o kQ [Q ]
ϕf

•  Therefore a plot of the left-hand side of the above equation

against [Q] should produce a straight line with the slope τ0kQ.
Such a plot is called Stern-Volmer plot.

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Quenching & Stern-Volmer Plot

Stern-Volmer plot, is shown below for the case of fluorescein
quenched by iodide ion (I-).
1.7

1.6 In this case, slope ~ 8 Lmol-1

Slope = kQ τ0 where kq is
1.5
the bimolecular quenching
1.4
rate constant and τ0 is the
I0F/I0/F

1.3 excited state lifetime in the

1.2 absence of quencher.
1.1

1.0
0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.07

Concentration of I- (M)

In the case of purely collisional quenching, also known as dynamic

quenching: I0/I = τ0/τ.

Hence in this case: τ0/τ = 1 + kq τ0[Q]

In the fluorescein/iodide system, τ = 4ns and kq ~ 2 x 109 M-1 sec-1

•  The fluorescence intensity and lifetime are both

proportional to the fluorescence quantum yield, plot of
If,0/I0 and τ0/ τ against [Q] should also be linear with
the same slope and intercept as
ϕf
= 1 + τ o kQ [Q]
ϕ
•  The quenching of tryptophan fluorescence by
dissolved O2 gas was monitored by measuring
emission lifetimes at 348 nm in aqueous solutions.
Determine the quenching rate constant for this
process

[O2]/(10-2 M) 0 2.3 5.5 8 10.8

Tau/(10-9 s) 2.6 1.5 0.92 0.71 0.57

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3 Common Mechanisms for

Bimolecular Quenching
1. Collisional deactivation:
S* + Q → S + Q (denoted before as M)
is particularly efficient when Q is a heavy species
such as iodide ion.

2. Resonance energy transfer:

S* + Q → S + Q*

3.  Electron transfer:

S* + Q → S+ + Q-
or S* + Q → S- + Q+

Energy Transfer Processes

•  (Forster theory,1952) Energy transfer is more efficient when:

1. The energy donor and acceptor are separated by a short

distance, in the nanometer scale.
2. Photons emitted by the excited state of the donor can be
absorbed directly by the acceptor.

•  The efficiency of energy transfer, ET, equals

φf R06
ET =1 − ET =
φ f ,0 R06 + R 6
Where R is the distance between the donor and the acceptor. R0
is a parameter that is characteristic of each donor-acceptor pair.

•  Fluorescence resonance energy transfer (FRET)

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Quenching by Energy Transfer

Electron transfer reactions

(Marcus theory)
•  The distance between the donor and acceptor, with electron
transfer becoming more efficient as the distance between
donor and acceptor decrease.

•  The reaction Gibbs energy, ∆rG, with electron transfer

becoming more efficient as the reaction becomes more
exergonic. (change for free energy is negitive)

•  The reorganization energy, the energy cost incurred by

molecular rearrangements of donor, acceptor, and medium
during electron transfer. The electron transfer rate is predicted
to increase as this reorganization energy is matched closely
by the reaction Gibbs energy.

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Complex photochemical processes

•  The overall quantum yield of a photochemical

reaction. (can be larger than 1)

•  Rate laws of complex photochemical reactions.

•  Photosensitization (no direct absorption).

Quantum yield of a complex

photochemical reaction
•  Overall quantum yield: the number of reactant
molecules consumed per photon absorbed:

For example: HI + hv → H. + I. chain reaction activation)

HI + H. → H2 + I.
I. + I. + M → I2 + M*

Here the overall quantum yield is two, because the

absorption of one photon destroys two reactant molecules HI.
Therefore, in a chain reaction the overall quantum yield can
be very large.

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The Photosynthesis of Hydrogen Chloride

Cl2 + H2 2HCl [no reaction in darkness]

Mechanism:
hν
Cl2 < 500 nm
2Cl Photochem. initiation

Cl + H2 HCl + H Dark reactions

H + Cl2 HCl + Cl
Chain reaction

H +H +M H2 + M* Recombination
reactions (chain
Cl + Cl + M Cl2 + M* is terminated)

Quantum yield is about 106 (explosion)

Photosensitization
•  Transfer of excitation energy from one molecule (the
photosensitizer) to another nonabsorbing species
during a collision.
•  Example: hydrogen gas containing trace amount
of mercury for the synthesis of formaldehyde:
H. + CO à HCO.
HCO. + H2 à HCHO + H.
HCO. + HCO. à HCHO + CO

•  Basis for Photodynamic therapy.

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Typical Example
When a sample of 4-heptane was irradiated for 100s with
313 nm radiation with a power output of 50W under
conditions of total absorption, it was found that 2.8 mmol
C2H4 was formed. What is the quantum yield for the
formation of ethylene?

Solution: First calculate the number of photons generated in the

interval 100s.

Then divide the amount of ethylene molecules formed by the amount of

photons absorbed.

N(photons) = P∆t/(hc/λ)
Ф = n(C2H4)*NA/N
= 0.21

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