PHOTOCHEMISTRY

It is the study of chemical reactions of molecules in electronically excited states produced by

the absorption of infrared (700 1000 nm), visible (400-700nm), ultraviolet (200 400) or
vacuum UV (100 200 nm) light. As a consequence of such excitation, bond making and
bond breaking as well as electron transfer and ionization are observed.

Quenching:

A quenching process is defined as one which competes with the spontaneous emission
process and thereby shortens the lifetime of the emitting molecule. These quenching reactions
are energy transfer or electron transfer processes. Quenching may be classified into three
types.They are,

1. Self-quenching: In self-quenching process the excited molecule A* loses its energy as

heat by collision with its own normal-molecule.

A* + A A + A + heat

2. Impurity quenching: In impurity quenching the excited molecule loses its energy as
heat by collision with the molecule of impurity present in the system.

A* + Q A + Q + heat

Q Quencher. If Q is an electron donor, then the reaction is reductive quenching and if Q is

an electron acceptor, then the reaction is oxidative quenching.

3. Solvent quenching: In solvent quenching the excited molecule A* loses its energy as
heat by collision with the solvent molecule.

A* + S A + S + heat

Initially the normal molecule A goes to an excited state by the absorption of incident

A A* Rate= Ia
radiation.
 The rate of formation of A* depends upon the intensity of incident radiation(I a).In the
absence of any quenching molecule the excited molecule A* is deactivated by the following
three processes

A* kf A + hvf Rate =kf [A*]0

kIC Rate = kIC[A*]0

A* A + heat
kISC Rate = kISC[A*]0
A* 3
A + heat

Where [A*]o is the concentration of the excited molecule A* in the absence of quenching
molecule.

Kinetics of Collisional Quenching:

Stern-Volmer equation Stern-Volmer equation is the kinetic pattern which accounts for
the quenching of the excited donor by the acceptor.

Under steady illumination, according to steady state approximation the rate of formation of
an excited molecule A* is equal to its rate of deactivation and the concentration of A*
remains constant.

=0

i.e., Ia = kf[ +

=[

The concentration of A* in the absence of any bimolecular quenching step is given as

[
(1)

Where Ia - rate of absorption or rate of formation of the activated molecule

kf rate constant for fluorescence

ki sum of rate constants of all unimolecular deactivation step

The quantum efficiency of fluorescence in the absence of quenching

fo=kf[A*]o /Ia

By substituting the value of [A*]o from eqn 1 we get

(2)

If another molecule Q is added to the solution which quenches the fluorescence by a

bimolecular quenching step

A* + Q A + Q Rate=kq[A*][Q]

Here [A*] is the concerntration of A* in the presence of quenching molecule.

Using steady state of approxiamation the rate of formation of A*=rate of deactivation of A*

=[

[ (
3)

In the presence of quenching molecule the quantum yield of fluorescence is given as

Substituting the value of [A*] from equation 3, we get

 ------4
The ratio of the two quantum yields is obtained by dividing equation 2 by 4

0f kf k +k + K ISC + k q [Q]
= X f IC
f k f + k IC + K ISC kf

= 1+

(5)

This eqn is Stern-Volmer eqn and k SV is called Stern-Volmer constant. Ksv is the ratio of
bimolecular quenching constant to unimolecular decay constant and has the dimension of
litre/mole.It implies a competition between the two decay pathways and has the character of
the equilibrium constant.

Calculation of Ksv

Stern-Volmer eqn is a linear in quencher concerntration.The plot of fo/ f against [Q]

must be a straight line with the slope=Ksv
Calculation of rate constant kq for quenching step:

The Stern-Volmer constant (6)

The actual life time of the fluorescence molecule in the absence of bimolecular quenching ()

is given by The eqn 6 may be written as

ksv = kq .

The value of is measured experimentally, the ratio of Ksv/ gives the rate constant k q for
the bimolecular quenching step. For efficient quencher Ksv=102-103 l mol-1 and =10-8S,then

This value of kq is almost equal to collision frequency (or encounter frequency). This shows
the quenching step is a diffusion controlled process.

The rate constant for quenching Kq can also be calculated from the condition of 50%
quenching. If [Q]1/2 is the concentration of the quencher when the solution is half quenched

Fron eqn 5

=1+
This eqn shows that the Ksv = reciprocal of [Q] 1/2, half-quenching concerntration or half
value concerntration Ch.

If kq is assumed to be diffusion controlled, the lifetime of unquenched molecule can be

obtained from knowledge of Ksv. For a strongly absorbing solution with fluorescence
lifetime=10-8 S and assuming diffusion controlled quenching, the half quenching
concentration.[Q]50% is of the order of 0.01M and for 10% quenching, .[Q] 10% =0.001M. But if
=10-2S, [Q]50%=10-8 M. This explains the sensitivity of the long-lived phosphorescent state to
traces of impurities.