Photoluminescence:

Any luminescence that is induced by the absorption of photons is called

photoluminescence.
Photoluminescence is light emission from any form of matter after the
absorption of photons (electromagnetic radiation). It is one of many forms
of luminescence (light emission) and is initiated by photoexcitation (i.e.
photons that excite electrons to a higher energy level in an atom), hence the
prefix photo-. Following excitation various relaxation processes typically occur
in which other photons are re-radiated. Time periods between absorption and
emission may vary ranging from short femtosecond-regime up to milliseconds
for Phosphorescence processes in molecular systems; and under special
circumstances delay of emission may even span to minutes or hours.

Fluorescence:
Certain substances when exposed to light or certain other radiations absorb the
energy and then immediately start re-emitting the energy. Such substances are
called fluorescent substances and the phenomenon is called fluorescence.
A process in which a part of energy (UV, Visible) absorbed by a substance is
released in the form of light as long as the stimulating radiation is continued. The
fluorescence emission took place from a singlet excited states (average lifetime:
from <10-9 to 10-7 sec).
It may be pointed that different substances shows the phenomenon of
fluorescence with different wavelengths.
Examples of fluorescence are solutions of fluorescein and eosin When their
solution are placed in light, they show fluorescence from green to violet colour,
vapour of sodium, mercury, iodine etc. also show this phenomenon. Thus,
fluorospar (CaF2) show fluorescence with blue light, chlorophyll (green pigment)
with red light, uranium glass with green light and so on.

Phosphorescence:
There are certain substances which continue to glow for some time even after the
external light is cut off. Thus, phosphorescence is a slow fluorescence.
A process in which energy of light absorbed by a substance is released relatively
slowly in the form of light. The phosphorescence emission took place from a
triplet excited states (average lifetime: from 10-3 to 102 sec).
Mechanism of Fluorescence and Phosphorescence
Electronic transitions are responsible for luminescence .
• When the system absorbs energy, electrons are excited and are lifted into a
higher energetic state. Such electronically excited states are unstable.
• Electrons drop back to their ground states. At the same time, the excitation
energy is released again. One distinguishes between radiative and non-
radiative decay processes.
o Most of the time, the decay is non-radiative, for example through
vibrational relaxation, quenching with surrounding molecules, or internal
conversion (IC). These processes will be explained in detail later.
o Sometimes, a radiative decay can occur in form of fluorescence and
phosphorescence. The energy is emitted as electromagnetic radiation or
photons. The emitted light has a longer wavelength and a lower energy
than the absorbed light because a part of the energy has already been
released in a non-radiative decay process.
Both fluorescence and phosphorescence are spontaneous emissions of
electromagnetic radiation. The difference is that the glow of fluorescence stops
right after the source of excitatory radiation is switched off, whereas for
phosphorescence, an afterglow with durations of fractions of a second up to hours
can occur.
To compare the photo-physical processes behind both phenomena, there are some
facts about electrons that are helpful for understanding:

Spin multiplicity: spin multiplicity of a state is given by (2S + 1) where S is

the total electron spin. Electrons are particles that have a so-called spin and a spin
quantum number. This can have two different values, namely either +1/2 or –1/2.

If S = 0, then spin multiplicity = 1, Such an electronic state is called Singlet state.

If S = 1, then spin multiplicity = 3, Such an electronic state is called Triplet state.
First step: It is the transition from higher excited singlet states (S2, S3, …) to
the lowest excited singlet state S1.This is called internal conversion (IC).
It is a non-radiative process and occurs in less than 10-11 second.

Now from S1 the molecule returns to ground state by any of the following paths.

Path I : The molecule may lose rest of the energy also in the form of heat so that
the complete path is non-radiative or radiation less transitions.

Path II: Molecule releases energy in the form of light or uv radiation. This is
called Fluorescence
Path III : Some energy may be lost in transfer from S1 to T1 in the form of heat.
It is called intersystem crossing (ISC). This process involves transition between
states of different spins (parallel to antiparallel), ie, different multiplicity. This
path is non-radiative.

Path IV: After ISC, the molecule may lose energy in the form of light in going
from the excited triplet state to the ground state. This is called phosphorescence.

Both fluorescence and phosphorescence emit radiations of shorter frequencies or

larger wavelength than the incident radiation or exciting radiation because some
part of radiation absorbed by the molecule is dissipated in the form of heat during
the non-radiative transitions. This is called Stokes shift.
Since triplet states are lower in energy than excited singlets, phosphorescence
occurs at a longer wavelength than fluorescence.

Applications:
Clinically compatible time-resolved fluorescence spectroscopy and imaging
systems developed by several research groups have shown that fluorescence can
be employed to know about the diseased tissues in patients.
Some important applications in the field of medicine are listed below:
1)The analysis of the concentration of riboflavin (Vitamin B.) in chloroform has
been carried out.
2) Use of fluorescent microscopes and fluoroscope used in X-ray diagnosis help
in testing the condition of food stuff and detecting ring worms etc.
3) Fluorescence is helpful in tissue characterization and diagnosis.
4) Applications of time-resolved fluorescence to diagnosis of humans such as:
pathologic conditions in
(a) diagnosis of cancer of the gastrointestinal (GI) tract, bronchi/lung. skin, head
and neck, and brain,
(b) ophthalmic pathologies, and
(c) atherosclerotic cardiovascular disease.
5) The potential role of fluorescence is in the diagnosis and treatment of tumors

Applications of fluorescence in other fields are as under:

1) For lighting purposes in fluorescent tubes: Mercury arc producing large
proportion of ultra-violet light is used in a tube coated with fluorescent salts
which gives visible light.
2) By mixing fluorescent dyes with coloured paints, the fluorescence of the dye
helps the light reflected by the paint to produce extra-ordinary brightness and
luster. These materials are used as road signs.
3) In industry for testing and identifying materials, e.g. in rubber industry.
4) In television- the cathode stream of the photo-electric effect is made visible in
the cathode ray tube by adding ZnS to which a little Ni is added to cut off
phosphorescence which otherwise makes the picture blurred.
5) A fluorescent dye is used as whitener for washing cloth when mixed with
washing powder.

Differences between Fluorescence and Phosphorescence

Fluorescence
It is the radiation emitted in a transition
between states of same multiplicity
Its decay period is very short, 10-9 -10-7 sec.
Its spectrum is mirror image of the
absorption spectrum.
It can be observed in solution at room
temperature.
It is exhibited by some elements in vapour
state.
Examples: uranium, petroleum, organic
dyes, chlorophyll, CaF2, etc.
Phosphorescence
It is the radiation emitted in a transition
between states of different multiplicity
Its decay period is much longer, 10-3 -100 s.
Its spectrum is not mirror image of the
absorption spectrum.
It is not observed in solution at room
temperature.
It is rarely observed in gaseous or vapours.
Examples: ZnS, sulphides of alkaline earth
metals.