What is

Photochemis
try?

Prof. Dr. A. Sreekanth

Department of Chemistry
National Institute of Technology,
Tiruchirappalli
 CHARACTERISTICS OF LIGHT
 Light = band of waves of different wavelengths Increase in frequency (energy)

Increase in wavelengths (nm)

(Light) Electromagnetic spectrum important for
photochemistry:
o Difference between photochemical and thermochemical reactions
ENERGY TRANSITIONS:
• Molecules absorb radiation by increasing internal

energy: Internal energy  electronic, vibrational, &

rotational states

• Energy requirements:

(3). Rotational (2). Vibrational (1). Electronic

transitions transitions transitions

 Far-IR-Mic (> 2000  Near-IR (700-2000  UV-vis ( 400-700

 Typical Molecular
Typical electronic
vibrations
transitions:

Typical Molecular
rotations
What Happens When Radiation Hits a Molecule?
 o LAWS OF PHOTOCHEMISTRY
1) Grothus–Draper Law (qualitative aspect)
It is only the absorbed light radiations that are effective in producing a
chemical reaction.

2) Stark-Einstein Law of Photochemical Equivalence

Stark and Einstein (1905) studied the quantitative aspect of
photochemical reactions by application of Quantum theory of light.

Illustration of Law of Photochemical

equivalence; absorption of one
photon decomposes one molecule.
 o In a photochemical reaction, each molecule of the
reacting substance absorbs a single photon of radiation
causing the reaction and is activated to form the products.

o In practice, we use molar quantities. That is, one mole of A absorbs

one mole of photons or one einstein of energy, E. The value of E
can be calculated by using the expression given below:
o Primary and Secondary reactions:
The overall photochemical reactionmay consist of :
(a) a primary reaction: proceeds by absorption of radiation.

(b)secondary reaction: is a thermal reaction which occurs subsequent to

the primary reaction.
For example, the decomposition of HBr occurs as follows :

o Evidently, the primary reaction only obeys the law of photochemical equivalence strictly.
The secondary reactions have no concern with the law.
 o Quantum yield (or Quantum efficiency)
(ᶲ)

o For a reaction that obeys strictly the Einstein law, one

molecule decomposes per photon, the quantum yield φ = 1.

o When two or more molecules are decomposed per photon, φ > 1 and
the
reaction has a high quantum yield.

o If the number of molecules decomposed is less than one per photon, φ <
1 the reaction has a low quantum yield.
 o Causes of high quantum yield
The chief reasons for high quantum yield are :
(1) Reactions subsequent to the Primary reaction:

(2) A reaction chain forms many molecules per photon:

 A reaction chain steps:
1) Initiation……………….
2) Self-propagating……

The number of HCl molecules

formed for a photon of light is very
high. The quantum yield of the
3) Termination…………. reaction varies from 104 to 106
 CALCULATION OF QUANTUM YIELD
By definition, the quantum yield, , of a photochemical reaction is expressed as
:

Thus we can calculate quantum yield from :

(a) The amount of the reactant decomposedin a given time and

(b) The amount of radiation energy absorbed in the same time

o The radiation energy is absorbed by a chemical system as photons.

Therefore we should know the energy associated with a photon or a mole of
photons.
EMISSION:
• An electron jump from
higher into s aorbita
and
a releases lowe
(emits)
l, a
photon of energy
r equal
to the difference (∆E =
hv).

• Luminescence
(emission of light) works on
the basis that if a
de-
molecule issomeho an
excited above
excite
its ground w
state, then it d
excess
release
must energy
non- as
either
radiative radiative or
energy.
Selection Rules in Photochemistry

🔹 Spin Allowed Transitions

•Condition: ΔS = 0 (spin does not change).
•Example: Singlet → Singlet or Triplet → Triplet.
•These transitions are strong (high intensity absorption).
•Probability of transition is high.

🔹 Spin Forbidden Transitions

•Condition: ΔS ≠ 0 (spin changes).
•Example: Singlet → Triplet or Triplet → Singlet.
•These transitions are weak (low intensity absorption).
•Probability of transition is very low.
•Still possible due to spin–orbit coupling.

Spin–Orbit Coupling
•It is the interaction between an electron’s spin (S) and its orbital motion (L).
•Causes mixing of singlet and triplet states.
•Makes spin-forbidden transitions partly allowed.
•Stronger in atoms with high atomic number (heavy atom effect).
•Important for phosphorescence (T₁ → S₀) to occur.
Kasha’s Rule
•Emission of light occurs from the lowest excited state of a given multiplicity.
•Means:
• Fluorescence → always from S₁ → S₀.
• Phosphorescence → always from T₁ → S₀.
1. Reason: molecules lose extra energy quickly by internal conversion and vibrational relaxation, before
emission.
2. Even if excitation was in S₂, S₃, etc., emission comes only from S₁ (for singlet) or T₁ (for triplet).
 Jablonski diagram (JD)
 A good starting point for a discussion
of luminescence (fluorescence or
phosphorescence) principle is a
simplified Jablonski diagram.

• The Jablonski diagram is employed to

represent the energy levels of a molecule.
As depicted in JD, S0, S1 and S2 represent
ground, first and second singlet electronic
states, respectively, whereas T1 and T2
describe first and second triplet
electronic states, respectively.

• Each electronic energy level of a

molecule also has numerous vibrational
(v) and rotational (n) energy sublevels.
 (JD)
10-11 s
Absorbance

10-9 to 10-7 s
energy

10-15 s 10-3 to 102s

PHOTOPHYSICAL PROCESSES:
o If the absorbed radiation is not used to cause a chemical change, it is re-
emitted as light of longer wavelength. The three such photophysical processes
which can occur are :
(1) Fluorescence (2) Phosphorescence (3) Chemiluminescence
o Fluorescence
 Process at which certain molecules (or atoms) when exposed to light radiation
of short wavelength (high frequency), emit light of longer wavelength.

 Substance that exhibits fluorescence is called fluorophore.

 Florescence stops as soon as the incident radiation is cut off.

Examples:
(a)a solution of quinine sulphate on exposure to visible light, exhibits blue
fluorescence.
(b) a solution of chlorophyll in ether shows blood red
fluorescence.
o Fluorescence depends on:
1. pH
2. Solvent
3. Temperature
4. Salts
5. Concentration
 Phosphorescenc
e
 When a substance absorbs radiation of high frequency and emits light even after
the incident radiation is cut off, the process is called phosphorescence.

 The substance which shows phosphorescence is called phosphorescent substance.

 Phosphorescence is chiefly caused by ultraviolet and visible light. It is generally

shown by solids.
Examples:
(a) Sulphates of calcium, barium and strontium exhibit phosphorescence.

(b) Fluoresce in boric acid shows phosphorescence in the blue region at 570nm wavelength.

o Phosphorescence could be designated as delayed fluorescence.

Fluorescence : Emission of a photon from a singlet excited state to a
singlet ground state, or between any two energy levels with the
same spin, is called fluorescence. Fluorescence, decays rapidly after
the excitation source is removed. Lifetime of the electron is only 10–9 to
10–7 s

Phosphorescence : Emission between a triplet excited state and a

singlet ground state is called phosphorescence. phosphorescence
may continue for some time after removing the excitation source.
Lifetime for phosphorescence ranges from 10–3 to 102 s.

CHEMISTRY PHOTO CHEMISTRY

When a molecule absorbs a photon of energy, electronic transition occurs (Su or S2 or S1).
A molecule in S1 state undergo one of the following four energy
degrading (decay) processes to the ground state.
(i) The molecule can undergo chemical reaction or return to the ground state by emission
of light by a process called fluorescence and generally occurs with in 10-9 to 10-6 sec.
(ii)It may return to ground state (S0) by non radiative process in which excess energy
of the excited state is shuffled into vibrational modes.
(iii) S1 may undergo chemical reactions.
(iv) The molecule may undergo spin inversion to the triplet state (spin unpaired) by a
process as ”intersystem crossing”, Which is a radiation less process.

CHEMISTRY PHOTO CHEMISTRY

 Chemiluminescen
o ce:
The emission of light as a result of chemical action is called chemiluminescence.
The reaction is referred to as a chemiluminescent reaction.

o Chemiluminescent reaction is the reverse of a photochemical reaction which

proceeds by absorption of light.

o The light emitted in a chemiluminescent reaction is also called ‘cold light’ because it
is
produced at ordinary temperature.

o In a chemiluminescent reaction, the energy released in the reaction makes the product
molecule electronically excited. The excited molecule then gives up its excess
energy as visible light while reverting to ground state.
 Chemiluminescence of Fireflies and luminol

Examples:
(a)The glow of fireflies due to the aerial oxidation of luciferin (a protein) in the
presenceof enzyme luciferase.
(b) The oxidation of 5-aminophthalic cyclic hydrazide (luminol) by hydrogen
peroxide in alkaline solution, producing bright green light.
 PHOTOSENSITIZED REACTIONS
o In many photochemical reactions the reactant molecule does not absorb
the radiation required for the reaction. Hence the reaction is not possible.

o In such cases the reaction may still occur if a foreign species such as
mercury vapour is present.
o A species which can both absorb and transfer radiant energy for activation
of the reactant molecule, is called a photosensitizer. The reaction so caused is
photosensitized
called a reaction.
Reaction between H2 andCO:
Hg + hv →Hg* Hg + hv → Hg* Primary absorption
Hg* + A → A* + Hg Hg* + H2 → 2H * + Hg Energy transfer
H + CO →HCO

Some glyoxal, CHO-CHO, is also formed by dimerization of formyl radicals,

HCO.
Application of photochemistry:-

1. Light Emitting Diodes (LEDs)

• Principle: Electroluminescence – Conversion of electrical energy directly into light.
• Design & Construction:
• Built around a p-n junction semiconductor chip (e.g., Gallium Nitride).
• p-type: Semiconductor with positive charge carriers ("holes").
• n-type: Semiconductor with negative charge carriers (electrons).
• Encased in an epoxy lens for protection and light focusing.
• Working:
• A voltage is applied across the p-n junction.
• Electrons from the n-side gain energy, cross the junction, and recombine with holes on the p-side.
• Upon recombination, electrons drop to a lower energy level, releasing the energy difference as
a photon of light.
2. Photovoltaic Cells, Panels, and Arrays

• Principle: The Photovoltaic Effect – Conversion of light energy directly into electrical energy.
• Design & Construction of a Cell:
• Core is a p-n junction semiconductor, almost always Silicon.
• Thin anti-reflective coating to maximize light absorption.
• Metal grid on top and a full back contact to collect current.
• Working of a Cell:

• Sunlight (photons) strikes the cell.

• If a photon has enough energy, it is absorbed and knocks an electron loose, creating a mobile electron-hole
pair.
• The built-in electric field of the p-n junction forces the electron toward the n-side and the hole toward
the p-side.
• When an external circuit is connected, electrons flow from the n-side to the p-side, creating Direct Current
(DC) electricity.
• From Cell to System:
• Cell: Basic unit (~0.5V).
• Module/Panel: Multiple cells connected in series (to increase voltage) and protected under glass.
• Array: Multiple panels interconnected to form a power-generating system for homes, buildings, or power
plants.