Photoluminescence

Course Instructor Presented By

Dr. A. Subramania Prashant Kumar
Reader M.Tech, NAST,
2
nd
SEM


What is photoluminescence ?
It is a process in which a substance
absorbs photon (electromagnetic
radiation) and then reradiates
photons.
Quantum mechanically this can be
described as an excitation to a higher
energy state an then return to a
lower energy state accompanied by
the emission of a photon.
Monomolecular Physical processes
Internal
Conversion
Fluorescence
Delayed
Fluorescence
Intersystem
Crossing
Phosphorescence
Nonradiative
Transition
Radiative
Transition
Phototoluminescence
Electronic spin states

Fluorescence
It is a prompt spin allowed emission of radiation within the vibrionic state
of same spin multiplicity.
Mechanism of Fluorescence
Electrons are activated by light from
HOMO to LUMO.
When the light is removed then they
fall back to homo and gives light
which is known as fluorescence.
This radiation has the life time of
10^-9 to 10^-6 seconds (short lived
)

Stokes Shift
Compounds Exhibiting
Fluorescence
Usually aromatic compounds.
Specially favored for rigid structures.

N
H
N
H
2
C
N
O
Zn
2
Quinoline Indole Fluorine
8-hydroxy quinoline
Variables affecting
Fluorescence
Quantum yield
Concentration of compounds
Structure of compounds
Temperature pH and solvent effects.
Quantum yield or efficiency
It is defined as the ratio of number of molecules that luminese to
that of total number of excited molecules.
This is basically efficiency of fluorescence.
d pd isc ic ec F
F
F
k k k k k k
k

+ + + + +
= |
k
ec
= external conversion rate constant(S
1
S
0
)
k
ic
= internal conversion rate constant (S
1
S
0
)
k
isc
= intersystem crossing rate constant (S
1
T
1
)
k
pd
= predissociation constant
k
d
= dissociation rate constant
Quantum yield increases by decreasing the factors that promote other
deactivation process
Effect of concentration on
fluorescence
Fluorescence of crude oil
At the lower concentrations fluorescence is linear but there are deviations
due to absorbance becoming significant factor and by self quenching and self
absorption
Effect due to the structure of
compounds
Usually aromatic compounds exhibit
fluorescence.
Low energy pi-pi* transition.
Quantum yield increase with the
number of rings and degree of
compensation and thereby increasing
fluorescence.
Temperature solvent and pH
effects
As the temperature decreases
florescence increases due to
deactivation.
As viscosity increases fluorescence
increases.
AS O2 is dissolved fluorescence
increases.
Fluorescence is pH dependent for
acidic or basic substituents.
Applications of fluorescence
In the detection of inorganic species by adding a fluorophore

Ion Reagent Absorption (nm) Fluorescence (nm) Sensitivity (ppm) Interference
Al
3+
Alizarin garnet R 470 500 0.007
Be, Co, Cr, Cu, F
-
,NO
3-
, Ni, PO
4
-3
,
Th, Zr

F
-
Al complex of Alizarin
garnet R (quenching)
470 500 0.001
Be, Co, Cr, Cu, F
-
,Fe, Ni,PO4-3, Th,
Zr


B
4
O
7
2-
Benzoin 370 450 0.04
Be, Sb
Cd
2+
2-(0-Hydroxyphenyl)-
benzoxazole
365 Blue 2
NH
3
Li
+
8-Hydroxyquinoline 370 580 0.2
Mg
Sn
4+
Flavanol 400 470 0.1
F
-
, PO
4
3-
, Zr
Zn
2+
Benzoin - green 10
B, Be, Sb, colored
ions
Phosphorescence
It is the spin forbidden emission of
radiation between vibrionic states of
different spin spin multiplicity
generally from T to S state.
Stoke's shift is more in the case of
phosphorescence.
Example of molecule showing
phosphorescence is phenenthrene.

Phosphorescence Quantum
Yield
Product of two factors:
fraction of absorbed photons that undergo
intersystem crossing.
fraction of molecules in T1 that phosphoresce.

|
|
.
|

\
|
+
|
|
.
|

\
|
+
=
k' k
kp
k k
k

nr F nr F
isc
F
|
Where Knr = nonradiative deactivation of S1
Knr = nonradiative deactivation of T1
Condition for phosphorescence
k
isc
> k
F
+ k
ec
+ k
ic
+ k
pd
+ k
d
k
P
> k
nr
Phosphorescence: More Stokes
Shift
The life time of phosphorescence is from 10^-3
to 1000 seconds (long lasting)
The rate of phosphorescence also depends upon
quantum yield, concentration and temperature as
fluorescence.
Material that can produce phosphorescence often
contains zinc sulfide, sodium fluorescin,
rhodamin. The majority of phosphorescence is
often used in drugs in phermaceutical yield.
Some common drugs that have phosphorescence
property include aspirin, benzoic acid, morphine
and dopamine.
Phosphorescence is also used to analyze water,
air and chemical pollutions.

Some points and applications for phosphorescence
References
Organic photochemistry : A visual
approach - Jan Kopechy
Chemwiki.udavis.edu
Acknowledgement
Dr. A Subramania Sir


Thanks