CHE 420E: PHOTOCHEMISTRY

Credit hours: 3

Course Purpose
The purpose of the course is to introduce learners to the study of chemical reactions that proceed with absorption of
light by atoms or molecules

Course Content
Einstein Law, quantum efficiency, molecular photochemistry; Types of excited states, distinctive properties of
excited states; Fluorescence, phosphorescence, internal conversion; Intersystem crossing; Lifetimes; photochemical
reactions; unimolecular reactions of excited states, isomerizations, dissociations, charge transfer; Bimolecular
sensitized reactions, triplet states; Atmospheric reactions; Applications of photochemical reaction to the synthesis of
naturally occurring systems, food preservation, production of industrial and health care products.

Objectives
The objectives of this course are:
 To train learners in the study of chemical reactions that proceeds with absorption of light
 To equip learners in applications of photochemical reactions
Expected Learning Outcomes
By the end of the course the learners should be able to:
 Discuss the Einstein’s law, molecular photochemistry, fluorescence, phosphorescence
 Discuss photochemical reactions
 Describe bimolecular sensitized reactions
 Discuss the applications of photochemical reactions

Teaching and Learning Methods

Lecture, Discussion, Practicals, Exercises, Tutorials

Mode of Assessment
Type Weighting (%)
Continuous Assessment Tests 30%
Examination 70%
Total 100%

Instructional Material / Equipment

Chalk and Chalkboard, Pen/Whiteboard, Power Point/LCD, Laboaratory manuals, Laboratory equipment and
Apparatus.

Course Text / References

Yadav, M. (2008).[Link] publishers and distributors
Wardle, B. (2010). Principles and Applications of Photochemistry. John wiley and sons
Rohatgi-mokherjee, M. M. (1978). Fundamentals of Photochemistry. New age international

Turro, N.J. (1991) Modern Molecular Photochemistry, Sausalito: University Science, 628 p.
Wayne, C.E., Wayne, R.P. (1996) Photochemistry, Oxford: Oxford University Press, 96 p.
CHE 420E: PHOTOCHEMISTRY

Definition

Photochemistry is the study of chemical reactions, isomerizations and physical behavior that occur under the
influence or effect of visible and/or ultraviolet light.
-It is used to describe a chemical reaction caused by absorption of ultraviolet (wavelength from 100–
400 nm), visible light (400–750 nm) or infrared radiation (750–2500 nm).
-Photochemical reactions - reactions brought by light radiations.
-When a molecule absorbs a photon of light, its electronic structure changes, therefore it reacts differently with other
molecules. The energy that is absorbed by a molecule from light can result in photochemical changes in the
absorbing molecule, or in an adjacent molecule (e.g., photosensitization).
-The energy can also be given off as heat i.e. fluorescence, or as lower energy light, i.e. Phosphorescence, in order
to return the molecule to its ground state.

The Basic Laws of Photochemistry

1. The First Law of Photochemistry (the Grotthuss-Draper law)

-States that light must be absorbed by a compound or molecule for photochemical reaction to occur. If light of a
particular wavelength is not absorbed by a system, no photochemistry will occur, and no photobiological effects will
be observed, no matter how long one irradiates with that wavelength of light.
-According to this law,all light radiations are not bringing chemical reaction. Some increases the Kinetic engery of
the molecule while some are re-emitted (i.e. fluorescence)

2. The second law of photochemistry (the Stark-Einstein law/Einstein law/ photo-equivalence law)

-States that for each photon of light absorbed by a chemical system, only one molecule is activated for a
photochemical reaction. Each molecule of absorbing substance absorb one photon (or quantum) of the radiation in
primary process.
This law was derived by Albert Einstein during his development of the quantum (photon) theory of light.
A molecule acquire energy by absorbing photon as,

A + hν A*

Thus energy of photon is,

E = hν = h c /λ,
Where ν = frequency of absortbing photon,
h=plank’s constant=6.624 X 10-34 J.s
c = speed of light (3 · 10 8 ms-1 )
λ = wavelength

The Einstein’s Equivalency Principle is that one particle of a chemical substance can absorb only one photon from a
light beam: ∆E = h ν

For one mole: ∆E = Nh ν

N = Avogadro’s number (6.02 X 1023 )

Differences between photochemical and thermal reactions

Photochemical reactions Thermochemical reactions

[Link] involve the absorption of light These involve either absorption or evolution of heat
2. Take place in presence of light Take place in dark or in presence of light
3. They are independent of temperature They are dependent of temperature
4. Rate of reactions is dependent on the Rate of reactions is not affected by the intensity of light
 intensity of the light absorbed.
5. The free energy change is negative or The free energy change is always negative
positive
(Quantum efficiency)Quantum Yield (Φ)

 Is defined as the ratio of number of molecules reacting in a given time to the number of quanta radiation
absorbed in the same time.

Φ = Number of molecules undergoing the process in a given time

Number of (Einstein) quanta absorbed in the same time

Φ= Rate of Chemical reaction

Number of (Einstein) quanta absorbed in the same time

In an idealized system the quantum yield should be unity. For several reactions, Φ = 1, for many reactions Φ ˃ 1,
while otherS Φ < 1.

Reasons for unique Quantum yield

According to Einstein law of photochemical equivalence, in primary process each molecule absorbs one quanta.
Hence Quantum yield is unity

Reasons for high Quantum yield: Φ > 1

-The product of primary process may collide with the second molecule and transfer energy, second to third and so
on. Thus chain reaction starts and number of reacting molecule will be high.
-It’s also due to formation of intermediate product which act as a catalyst.
-Exothermic reaction may activate more molecules.
(E.g. Hydrogen and halogen reaction)

Reasons for low Quantum yield: Φ < 1

-Deactivation of activated molecule may occur in some reactions in primary process before transfer to product.
-The product formed in primary process may react back to form reactants.
(E.g decomposition of HI and HBr,polymerization of anthracene).

Factors affecting Quantum yield

1. All primary photochemical process is [Link],quantum yield increases with temperature.
2. Energy absorbed by molecule is inversely proportional to wavelength .Thus ,quantum yield will be higher at
the lower wavelengh and viceversa.
3. Quantum yield increases with light intensity and viceversa.
4. Addition of inert gas in photochemical reaction-increases quantum [Link] causes induced pre-dissociation
which will increase the number of starting chains.

ABSORPTION OF LIGHT (RADIATION)

 Absorption: radiation selectively absorbed by molecules, ions, or atoms, accompanied by their excitation (or
promotion) to a more energetic state.
 Emission: radiation produced by excited molecules, ions, or atoms as they relax to lower energy levels.
The term radiation includes radio-waves, x-rays, gamma rays and also beams of particles like neutrons, electrons
and protons. The study of photochemistry helps us to know the changes when a molecule absorbs radiations.

When a monochromatic or heterogeneous light (I0 ), is incident upon a homogeneous medium, a part of it is
absorbed (Ia ), a part is reflected(Ir ) and remaining is transmitted (It ). We can write, I0 = Ia + Ir + It . For
comparison cell Ir is very small. Hence, I0 = Ia + It .

I
Transmittance (T), is defined as: T=
Io

where I is the light intensity after it passes through the sample and Io is the initial light intensity. The relation
between absorbance, A and transmittance T is:

I
A = -log T = - log ( ).
Io

Absorption of light by a sample:

I
 Transmittance ,T = , Absorbance, A = -log10 T = log10 I0/I
Io

A is linear vs. b!
(A preferred over T

Phenomenological (macroscopic) laws of absorption

i. The Lambert’s law:

When a beam of light is allowed to pass through a transparent medium, the rate of decrease of intensity with the
thickness of medium is directly proportional to the intensity of the light (incident radiation).

Mathematically, it may be stated as follows;

−dI −dI
α I i. e = k.I
dx dx
−dI
= - [Link]
I
k= Proportionality constant

I x
On integrating above eq. between respective limits, ∫ dI /I = k∫ dx
Io o

I I
ie. In = – k. x or 2.303 log10 = – k. x
Io Io
I k .x I
log10 = – , log10 = – a.x
Io 2.303 Io
I
= 10–a.x
Io
Where;
I0 = initial intensity before passing absorbing medium.
I = intensity after passing absorbing medium.
x = thickness of absorbing medium.
I
a = extinction coefficient. = transmission or transmittance (T).
Io
Io
Log = a.x = absorbance (A) or optical density (D).
I
Io
= opacity.
I

ii. The Lamberts-Beer’s law (or Beer’s law)

When a monochromatic radiation is passed through a solution of absorbing medium, the rate of decrease in the
intensity of radiation with thickness of absorbing medium is directly proportional to the intensity of the incident
radiation and concentration of the solution.

−dI −dI −dI

α I.c i.e = k’ I. c = – [Link]
dx dx I
On integrating above eq. between respective limits,

I x

∫ dI /I =k' . c ∫ dx
Io o
 I I
ie. In = – k’.c. x or 2.303 log10 = – k’.c. x
Io Io
I k ' .c. x I
log10 =- , log10 = – ε.c.x
Io 2.303 Io
Io
log = A or (D )= ε.c.x
I
Thus Absorbance,A = ε.c.x
Where:
I0 = initial intensity before passing absorbing medium.
I = intensity after passing absorbing medium.
x = thickness of absorbing medium.
ε = molecular extinction coefficient.

Limitations of the Beer-Lambert law

The linearity of the Beer-Lambert law is limited by chemical and instrumental factors. Causes of nonlinearity
include:

1. Deviations in absorptivity coefficients at high concentrations (>0.01M) due to electrostatic interactions

between molecules in close proximity.
2. Scattering of light due to particulates in the sample.
3. Fluoresecence or phosphorescence of the sample.
4. Changes in refractive index at high analyte concentration.
5. Shifts in chemical equilibria as a function of concentration.
6. Non-monochromatic radiation, deviations can be minimized by using a relatively flat part of the absorption
spectrum such as the maximum of an absorption band.
7. Stray light.

iii. The Bunsen-Roscoe Law of Reciprocity

States that a photochemical effect is directly proportional to the total energy dose, irrespective of the time required
to deliver the dose. This law is true for chemicals in a test tube, but the response of cells to radiation usually
involves a sequence of interacting biological reactions, making a linear "dose x time" relationship highly unlikely.

The electromagnetic spectrum

It is composed of different wavelengths of light having different photon energies.
Classified into the regions shown in the figure [Link].
 The regions of interest for photochemistry, i.e., visible and ultraviolet (UV), are only a small part of the full
electromagnetic spectrum.
 Longer wavelengths, e.g., far infrared - causes the vibrational excitation of molecules, resulting in heating.
 Shorter wavelength X-rays cause ionization.
 Electromagnetic spectrum

ELECTRON TRANSITIONS AND EXCITED STATES

Types of electron transitions:

1. Valence states

Occurring between bonding bonding and anti‐ bonding valence MOs – ππ* ‐ typically the only possibility for bright
i. s, p and n electrons (mostly organics)

states, i.e. photon absorption and emission occurs.

There are six types of this electronic transition;

- σ → σ * , σ → π * , π → π * , π → σ * , n → σ *and n → π * .
-The σ → σ *transitions correspond to absorption in the inaccessible far - ultraviolet, and both σ → π* and π → σ
*are obscured by the much stronger π → π * absorptions.

-n→π* ‐ often lower lying than π→π* but usually not directly accessible by light.
-π→σ* ‐ stable if bonds are elongated, may lead to dissociation

Electron transitions

ii. d and f electrons (inorganics/organometallics)

iii. Charge-transfer (CT) electrons - Charge - transfer transitions involve ligand -and metal - based levels, and
are classified as ligand - to - metal charge transfers (LMCTs) and metal - to - ligand charge transfers
(MLCTs). A metal complex absorb light and an electron is transferred from the d - orbitals of the metal to the
ligands or vice versa. In such transitions, because the electron moves through a large distance the transition
dipole moment will be large, resulting in an intense absorption. If donor and acceptor orbitals are spatially
separated, may lead to complete charge separation. LMCTs can occur in all complexes, including ones with
 empty or completely filled d - shells. MLCT is seen in complexes in which the ligands have low - lying empty
orbitals (e.g. CO and unsaturated ligands).
An example of MLCT is in the ruthenium (II) trisbipyridyl complex, written as Ru( bpy) 2+ 3 , where, on
photoexcitation, a d - electron is transferred from the ruthenium into the antibonding π * - orbitals of a
bipyridyl ligand and becomes delocalised over the extensive aromatic ligand system. This results in the intense
orange colour of the complex and a long excited - state lifetime

Table 1. Differences between Absorptions due to π → π *and n → π *transitions

Absorptions due to π → π *transitions Absorptions due to n → π *transitions

Occur at shorter wavelengths than do absorptions due to Occur at longer wavelengths than do absorptions due to
n → π *transitions π → π * transitions
Substitution moves the absorption to longer wavelength Substitution moves the absorption to shorter

Relatively strong absorptions with εmax values of ∼ 10 3 Relatively weak absorptions with εmax values of ∼1 to
wavelength

to ∼ 10 5 l mol − 1 cm − 1 ∼ 10 2 l mol − 1 cm − 1
The absorption band occurs at longer wavelength in a The absorption band occurs at shorter wavelength in a
polar solvent than in a nonpolar solvent (the absorption polar solvent than in a nonpolar solvent (the absorption

2. Rydberg states ‐ diffuse character, associated with higher quantum numbers

shows a red shift or bathochromic shift ) shows a blue shift or hypsochromic shift )

3. Core excited excited states – induced; by X‐rays.

Singlet and Triplet States (Two Electron Systems)

 Electrons are spin ½ particles.

 Singlet state: spins are paired, no net angular momentum (and no net magnetic field), one eigenstate ( |0,0 ).
 Triplet state: spins are unpaired, net angular momentum (and net magnetic field), three eigenstates (|1,-1  , |
1,0, |1,1 )

MOLECULAR PHOTOCHEMISTRY

Light - absorbing molecules contain antennae or functional groups known as chromophores or chromophoric
groups. They are responsible for the absorption of light. When the oscillating electromagnetic radiation encounters
an appropriate chromophore, an electron in the chromophore can be promoted to a higher - energy excited state.
When this electronic transition occurs, the absorbing chromophore undergoes an electric dipole transition and the
energy of the photon becomes part of the total energy of the excited - state molecule.

Example of chromophore: -OH and –NH2 on benzene chromophore.

Molecular energy levels and absorbance wavelength

s ® s* and s ® p* transitions: high-energy, accessible in vacuum UV (lmax <150 nm). Not usually observed in
molecular UV-Vis.
n ® s* and p ® s* transitions: non-bonding electrons (lone pairs), wavelength (lmax) in the 150-250 nm region.
n ® p* and p ® p* transitions: most common transitions observed in organic molecular UV-Vis, observed in
compounds with lone pairs and multiple bonds with lmax = 200-600 nm.
Molecules: electrons are in molecular orbitals (HOMO, LUMO)

Vibronic transitions in molecules

Absorption of ultraviolet and visible light by molecules results in electronic transitions in which changes in both
electronic and vibrational states occur. Such transitions are called vibronic transitions.

Absorption of radiation by molecules. Schematic diagram of the electronic ground state and the first excited
electronic state. The vertical arrows show vibronic transitions due to the absorption of photons.

Theoretical Models of Molecular Photochemistry

1. Born – Oppenheimer approximation

The total energy of molecules is made up of electronic energy and energy due to nuclear motion (vibrational and
rotational):

Et = Ee + Ev + Er

where the subscripts refer to the total energy, electronic energy, vibrational energy and rotational energy,
respectively. Because of the large differences between electronic, vibrational and rotational energies, it is assumed
that these can be treated separately. This assumption is known as the Born – Oppenheimer approximation.

The energy gap between electronic states is much greater than that between vibrational states, which in turn is much
greater than that between rotational states. As a result, we are able to adequately describe the effects of electronic
transitions within molecules by considering quantised electronic and vibrational states.

2. The Boltzmann distribution law

At thermal equilibrium the population of any series of energy levels is described by the Boltzmann distribution law.
If N 0 molecules are in the ground state then the number N 1 in any higher energy level is given by the equation:

N 1 (-∆E/RT)
=e
N0
Where;
 Δ E is the energy difference between the two energy levels,
 R is the gas constant (which has a value of 8.314 J K − 1 mol − 1 )
 T is the absolute temperature.

Calculations based on the Boltzmann distribution law show that,

- At room temperature, most molecules will be in the v = 0 vibrational state of the electronic ground state and so
absorption almost always occurs from, S 0 (v = 0) (Figure 2 ).
 3. Morse curve
It models the way in which the potential energy of the molecule changes with its bond length. At the points where
the horizontal lines meet the Morse curve, the energy is wholly potential.

The potential energy curve for a diatomic molecule.

4. Franck – Condon principle

Nuclei (is heavier) move much more slowly than the much - lighter electrons, so when a transition occurs from one
electronic state to another, it takes place so rapidly that the nuclei of the vibrating molecule can be assumed to be
fixed during the transition. This is called the Franck – Condon principle
A consequence of it is that an electronic transition occurs within a ‘stationary ’nuclear framework. Thus the
electronic transition accompanying the absorption of a photon is often referred to as a vertical transition or Franck –
Condon transition. Transitions between the vibrational levels in lower and upper electronic states will be most
intense when the two states have similar internuclear separations.

Franck-Condon Energy Level Diagram

Absorption of light by molecules;

1. Organic molecules
Molecular organic photochemistry have the π → π *and n → π *transitions, which produce (π, π * ) and (n, π * )
electronically - excited states, respectively. Two molecular orbitals in particular occurs; the highest occupied
molecular orbital (HOMO) is the ground - state molecular orbital of highest energy with electrons in it and the
lowest unoccupied molecular orbital (LUMO) is the ground - state molecular orbital of lowest energy with no
electrons in it.
Thus, the lowest energy transition in an organic molecule will be the HOMO → LUMO transition.

2. Linearly - conjugated molecules

When two carbon - to - carbon double bonds are present in a molecule, the effect on the electronic absorption
spectrum depends on the distance between them. In conjugated double bonds (the single and double bonds alternate)
the first absorption band is encountered at considerably longer wavelength than in a molecule with isolated (not
conjugated) C = C bonds. When two π molecular orbitals are sufficiently close, overlap can occur, giving two
delocalised π - orbitals, one of lower energy and one of higher energy. Likewise, two π * - orbitals give rise to two
delocalised π *molecular orbitals of different energies.

Selection rules of organic molecules

Transitions between energy levels in organic molecules are subject to certain constraints, referred to as selection
rules.
i. Spin selection rule: An electronic transition takes place with no change in the total electron spin –that is, Δ
S = 0 –hence singlet ↔ triplet transitions are forbidden or very weakly allowed.
ii. Orbital symmetry selection rule: According to the quantum theory, the intensity of absorption by
molecules is explained by considering the wavefunctions of the initial and final states (ψ and ψ *,
respectively). An electronic transition will proceed most rapidly when ψ and ψ * most closely resemble
each other; that is, when the coupling between the initial and final states is strongest.
The weak absorption of the n → π *transition compared to the π → π *transition is a consequence of the orbital
symmetry selection rule. Transitions involving a large change in the region of space the electron occupies are
forbidden. The orbital overlap between the ground state and excited state should be as large as possible for an
allowed transition. π -and π * - orbitals occupy the same regions of space, so overlap between them is large. The
orbital overlap between n -and π * - orbitals is very much smaller, as these orbitals lie perpendicular to each other.

The phasing of the molecular orbitals (shown as +/ −) is a result of the wavefunctions describing the orbitals
(+) shows that the wavefunction is positive in a particular region in space and (−) shows that the wavefunction
is negative.

Hence, according to the symmetry selection rule, π → π*transitions are allowed but n → π*transitions are
forbidden. However, in practice the n → π*transition is weakly allowed due to coupling of vibrational and
electronic motions in the molecule (vibronic coupling). Vibronic coupling is a result of the breakdown of the
Born – Oppenheimer approximation.

3. Inorganic complexes
The metal complexes of the d - block elements absorb light due to electronic transitions occurring between d -
orbitals of the metal species, or because of charge transfer within the complex.

For inorganic complexes there are three selection rules to consider;

i. Spin selection rule: The spin selection rule, Δ S = 0, specifies that there should be no change in the spin
multiplicity. Weak spin - forbidden bands may occur when spin – orbit coupling is possible. Spin -
forbidden transitions are more intense in complexes of heavy atoms as these lead to a larger spin – orbit
coupling.
ii. Angular momentum selection rule: Δ = ±1. Transitions that involve a change in angular momentum
quantum number by 1 (i.e. p ↔ d d ↔ f, for instance) are allowed. The important point here is that d – d
transitions are not allowed.
iii. Laporte selection rule: This is based on the symmetry of the complex. For complexes with a centre of
symmetry, this forbids a transition between energy levels with the same symmetry with respect to the
centre of inversion. The Laporte selection rule is not applied rigorously when ligands around the metal
disrupt the perfect symmetry or when the molecule vibrates to remove the centre of symmetry. The
interaction between electronic and vibrational modes is called vibronic coupling and means that d – d
transitions are observed but are often weakly absorbing. Complexes with tetrahedral symmetry do not have
a centre of inversion and so easier mixing of the levels is possible, giving more intense transitions.

THE PHYSICAL DEACTIVATION OF EXCITED STATES

Electronically - excited states of molecules are endowed with excess energy due to their formation by photon
absorption. These excited states are short - lived, losing their excess energy within a very short period of time
through a variety of deactivation processes and returning to a ground - state configuration. If the excited molecule
returns to its original ground state then the dissipative process is a physical process, but if a new molecular species is
formed then the dissipative process is accompanied by chemical change.

Photophysical relaxation processes may be classified as:

1 Intramolecular processes

i. Radiative transitions -which involve the emission of electromagnetic radiation as the excited molecule
relaxes to the ground state.
-Fluorescence and phosphorescence are known collectively as luminescence.
-Other examples of radioactive transitions; Chemiluminescence, Electroluminescence (EL).

-Radiative transition involves transition from S1→ S0 or T1→ T0 . It involves emission of transition.

Luminescence:
-The production of visible radiation due to some cause other than temperature. It is also called as cold-light.
-The two types of Luminescence are; Fluorescence and Phosphorescence.

Fluorescence:
- Atom or molecule returns from excited state to ground state, S1→ S0 with emission of radiation is called
Fluorescence.
- It is allowed transition and occurs in 10-8 second.
-The electronic transition of electron depends on wavelength of radiation. In case of atom, wave length of
fluorescence is same as absorbed radiation. This is called resonance Fluorescence.
In case of molecule, it is longer than absorbed radiation.
-When photochemically excited atom collides with another atom, intensity of Fluorescence radiation is decreased is
called quenching of Fluorescence.
Eg. Fluorite (CaF2), Uranium glass, fluorosein, eosin, chlorophyll etc.
Phosphorescence:
-The emission of transition from T1→ S0 is called Phosphorescence.
- It is forbidden transition.
-Even after incident light radiation is cut off there is emission of light for some time. It is also called slow
Fluorescence.
-The substance which shows Phosphorescence is called fluorescent substance.
-The name Phosphorescence is derived from phosphorous which glows in dark.
- Typical timescales for photon emission by phosphorescence are of the order of 10 − 3 – 10 2 s.
-Phosphorescence involves a spin - forbidden radiative transition between states of different multiplicity, usually
from the lowest vibrational level of the lowest excited triplet state, T 1 (v = 0) → S 0 + h ν
Eg. Organic dye, certain fungi sulphides of alkali metal etc.

Chemiluminescence:
-The emission of light as a result of chemical reactions at ordinary temperature is called Chemiluminescence.
-Chemiluminescence is reverse of photochemical reaction because light is given out instead of being absorbed.
-In Chemiluminescence excited product emits radiations of appropriate wavelength which is lie in visible region of
spectrum.
4 P + 5 O2 -------> 2P2 O5* (excited state)

2P2 O5*(excited state) --------> 2P2 O5 (ground state) + Radiation (Greenish glow).

- Oxidation of decaying wood containing certain forms of bacteria.

-The spectacular light emitted from fire-fly.
 Electroluminescence (EL):-
- Electroluminescence is a characteristic of a material that enables it to emit light in response to an electric current.
-EL is non-thermal conversion of electrical energy into light energy.
-This phenomena used in EL-lamps, LEDs and OLEDs.
-It is used in manufacture of Night signal light, decorative luminescent clothing, watch illumination, computer
monitors.

ii. Radiationless transitions

- It does not involve emission of any radiation hence called Non- radiative transition. It only involves emission of
heat. No emission of electromagnetic radiation accompanying the deactivation process.
- It involves transition from, S2 → S1 or S3 → S1 Or T2 → T1 or T3 → T1. E.g Internal conversion and
Intersystem crossing.

Internal Conversion (IC):-

-In this process energy loss in the form of heat. It involves transition from, S3 → S2 or S2 → S1 or T3 → T2 or T2
→ T1.
-It occurs in less than 10-11 second.
-Involves radiationless transitions between vibronic states of the same total energy (isoenergetic states) and the same
multiplicity. Internal conversion between excited states, e.g. S 2 to S1 is much faster than internal conversion
between S 1 and S 0.

-Typical timescales are of the order of 10 − 14 – 10 − 11 s (internal conversion between excited states) and 10 − 9 – 10 − 7
s (internal conversion between S 1 and S 0 ).
-This is the basis of Kasha ’ s rule, which states that because of the very rapid rate of deactivation to the lowest
vibrational level of S 1 (or T 1), luminescence emission and chemical reaction by excited molecules will always
originate from the lowest vibrational level of S 1 or T 1 .

Intersystem Crossing (ISC):-

-It involves transition from S3→ T3, S2→ T2 or S1→ T1.
-Intermolecular spin - forbidden radiationless transitions between isoenergetic states of different multiplicity.
-Has a timescale of the order of 10 − 11 – 10 − 8 s.

2 Intermolecular processes

Vibrational relaxation
-Involves transitions between a vibrational excited state and the v = 0 state, within a given electronic state.
-When excited molecules having excess vibrational energy undergo rapid collision with one another or collide with
other species such as solvent molecules, e.g. S 2 (v = 3) to (v2 = 0). The excess vibrational energy is dissipated as
heat.
-Typical time scales for the process are of the order of 10 − 13 – 10 − 9 s .

- Energy transfer - where the electronically - excited state of one molecule (the donor) is deactivated to a lower
electronic state by transferring energy to another molecule (the acceptor), which is itself promoted to a higher
electronic state. The acceptor is known as a quencher and the donor is known as a sensitiser.

- Electron transfer - considered as a photophysical process, involves a photoexcited donor molecule interacting
with a ground - state acceptor molecule. An ion pair is formed, which may undergo back electron transfer, resulting
in quenching of the excited donor.

The properties of excited states and their relaxation processes are conveniently represented by a Jablonski diagram
(The Theory of Molecular Fluorescence),
A typical Jablonski energy diagram:

 Notation: electronic states ,S2, S1 = singlet states, T1 = triplet state

 Vibrational levels associated with each state are denoted as v = 0, v = 1, v = 2, etc. in order of increasing
energy.
 Fluorescence is a singlet-to-singlet state process; phosphorescence converts the singlet to a triplet state via
intersystem crossing.
 Excitation directly to a triplet state is forbidden by selection rules
 Radiative transitions are drawn as straight arrows and radiationless transitions as wavy arrows.
 If an electronically - excited state is formed as a ‘ vibrationally - hot ’ excited molecule (with v > 0) then it will
undergo vibrational relaxation within that electronic energy level until it reaches the v = 0 level. The vibrational
relaxation within each electronically - excited state is drawn as a vertical wavy arrow.
 Radiationless transitions (internal conversion and intersystem crossing) between electronic states are iso
energetic processes and are drawn as wavy arrows from the v = 0 level of the initial state to a ‘ vibrationally -
hot ’(v > 0) level of the final state.

EXCITED - STATE LIFETIMES

It is from the S 1 (v = 0) state that any subsequent photophysical or photochemical changes will generally occur
(Kasha ’ s rule).

Excited Singlet - state Lifetime

The competing intramolecular photophysical processes that can occur from S 1 (v0) are fluorescence, intersystem
crossing and internal conversion, with first - order rate constants of kf, kisc and kic, respectively. Applying a standard
treatment of first - order chemical kinetics, the rate of disappearance of the excited S 1 molecules 1Jtotal, is given by:
1
Jtotal = -d[s1]/dt = (kf + kisc + kic) [s1] = ktotal[s1]
(the negative − sign shows that the excited S1 state decays with time; that is, its concentration decreases with time).
Solution of this equation gives the exponential decay form of the transient excited S 1 molecule:

[s1]t =[s1]0 exp(-t/1τ )

where [S 1 ] 0 is the concentration of excited S1 molecules at time t = 0 resulting from the initial exciting pulse, [S1 ] t
is the concentration of excited S 1 molecules at time t and 1τ is the excited singlet - state lifetime of the S 1 excited
state.

When t = 1τ :
[s1]t =[s]0 exp(-1) =[s]0 /e

Thus 1τ is given by the time for the concentration of S1 to decrease to 1/e of its original value, where 1/e = 1/2.718
= 0.3679 =36.8%.

The excited singlet - state lifetime, 1τ , is the time taken for the concentration of S 1 to decrease to 1/e of its
initial value .

Excited Singlet - state Radiative Lifetime

The excited singlet - state radiative lifetime, 1τ 0 , of S1 is the lifetime of S1 in the absence of any radiationless
transitions; that is, the only deactivation process is fluorescence. 1τ 0 is the reciprocal of the rate constant for
fluorescence, kf :

τ 0 = 1/ kf
1

Similarly, for the excited singlet - state lifetime:

τ = 1 /(kf + kisc + kic) = 1/ 1k total

1

where the sum of the rate constants for deactivation of the excited singlet state is given by:
1
k total =(kf + kisc + kic)

Since 1k total is greater than kf , the observed excited singlet - state lifetime is less than the excited singlet - state
radiative lifetime. 1τ only approaches 1τ 0 as intersystem crossing and internal conversion from S 1 become much
slower processes than fluorescence.

Now, the fl uorescence quantum yield , ɸf , is the fraction of excited molecules that fluoresce. This is given by the
rate of fl uorescence, Jf , divided by the rate of absorption, Jabs :

ɸf = Jf / Jabs

Under conditions of steady illumination, a steady state will be reached, where the rate of formation of excited
molecules, 1 R * , is equal to the rate of deactivation by the intramolecular processes:

Jabs =1Jtotal

Therefore:

ɸf = Jf / Jabs , ɸf = Jf / 1Jtotal
ɸf = kf[s1]/ 1k total[s1]

ɸf = kf / 1k total
Now:

τ 0 =1/ kf and so kf = 1/1τ 0

1

Similarly:

τ =1/ 1k total and so 1k total = 1/1τ

1

Thus:

ɸf = 1τ /1τ 0

An order - of - magnitude estimate of the radiative lifetime of S1 is given by:

τ 0 ≈ 10-4 /ɛmax

where τ 0 has units of s and ɛmax has units of l mol-1 cm-1 .

Thus, π - π * transitions with ɛmax of the order of 103 – 105 l mol-1 cm-1 give 1τ 0 of the order of ns-µs. For n - π*
transitions, ɛmax has values of the order 100 – 102 l mol-1cm-1 , giving 1τ 0 of the order of µs- ms.

Lifetimes of the T 1 Excited State

Similar considerations apply to the T1 triplet state as to the S1 singlet state. By analogy with the expressions for the
lifetimes of S1 , the values for T1 are given by:

3
τ 0 = 1/ kp

τ = 1/ktot = 1/ kp + k iscTS
3

An order - of - magnitude estimate of the radiative lifetime of T1 is given by:

τ 0 ≈ 10-4 /ɛmax
3

where τ 0 has units of seconds and ɛmax has units of l mol -1 cm-1 .

Note that S0 + h ν → T1 is spin - forbidden.

The molar - absorption coefficients for such transitions will be very small and so T 1 states will have a longer lifetime
than S1 states. In general, 3 (π , π * ) states have longer radiative lifetimes (1 – 10 2 s) than 3 (n, π * ) states (10 -4 –
10 -2 s).

Because excited triplet states decay more slowly than excited singlet states, it is much easier to determine the excited
triplet - state lifetime 3τ than 1τ .

PHOTOCHEMICAL REACTIONS

Photochemical reactions occur via two steps.

• First, a molecule AB absorbs a photon, and is excited to an excited electronic state (marked here with a *):
AB + hv ⇒AB*

– This can be thought of as a ”bimolecular” reaction involving a molecule and a photon. (But usually the photon
flux is included in an effective unimolecular rate constant J or j.)

• Next, the excited molecule undergoes one of many possible processes

1. Quenching (via collisions) back to the ground state
2. Dissociation to A + B
3. Chemical reaction e. g . isomerization
4. Ionization (loss of an electron)
5. Luminescense (re-emission of radiation) back to the ground state or some lower-energy excited state
6. Energy transfer -within the molecule to some other state, or energy transfer to another molecule
Often, e.g. ionization or dissociation occurs almost immediately, but sometimes the excited molecule AB* lives long
enough to react with other species.

Intermolecular Processes: Excited State Quenching

When a second molecule (a quencher, Q) interacts with a molecule in an excited state, new ways may be created for
the excited state species to lose its energy of excitation. Such interactions (collisions) can induce the loss of energy
in the form of heat, which is called physical quenching, or it can cause the energy to be transferred to the second
molecule with or without the transfer of an electron. The former is called energy transfer, and the latter, electron
transfer.
Formally, one can write:

When this kind of quenching occurs it reduces the concentration of the excited state more rapidly than if the
quencher were not present. Thus, fluorescence, which is proportional to the concentration of the excited state will
also be reduced.

From fluorescence of an excited state molecule, one can determine the concentration of a quencher, if its rate
constant of interaction with the excited state is known. Consider the molecule, M, that can decay by fluorescence,
intersystem crossing or internal conversion. Now add a fourth possibility, quenching. The reactions and rates are
then given by:
Note that the quenching reaction rate depends on 2 reactants, M and Q, and the rate constant is a bimolecular rate
constant.
Once again, one can make the steady state approximation, and compare the rate of fluorescence, k f[1M*] in the
presence of the quencher to the same quantity in the absence of the quencher. This leads to the following
relationship:

Where ;

 is the intensity, or rate of fluorescence, without a quencher;

 is the intensity, or rate of fluorescence, with a quencher;
 is the quencher rate coefficient;
 is the fluorescence lifetime of A without a quencher present,
 and is the concentration of the quencher.
This relationship is referred to as the Stern-Volmer equation.

Dissociation
Photons can sometimes break apart molecules. When this happens, it is called photodissociation. . The energy of an
absorbed photon may be sufficient to break molecular bonds creating two or more atomic or molecular fragments.
Molecules have chemical bonds that hold the atoms in them together with each other. Sometimes photons have
enough energy to break the bonds in a molecule. A photon of ultraviolet (UV) "light" has more energy than a photon
of visible light. UV photons can cause photodissociation more easily than visible light photons can.

A general photolysis reaction is written as,

A photodissociation reaction is a unimolecular reaction driven by light energy: which is the combination of two
steps:

 The first is the absorption of a photon.

 The second step, is an electronic transition to an unbound excited state. Kinetic energy may be imparted to the
photolysis fragments and/or they may be in an excited vibrational or electronic state. But in some cases it is
possible for photodissociation events to occur upon photon fluorescence, for example; H 2 in Jupiter's
atmosphere

Photodissociation in Earth's Atmosphere

 Photodissociation happens a lot in Earth's atmosphere. There are lots of chemical reactions in our air.
Photodissociation provides the energy for many of those reactions.

For example, photodissociation helps make smog. It also helps create ozone.

i. The photochemistry of stratospheric ozone is a good important example of photodissociation . Ozone (O 3) is

produced in the stratosphere from molecular oxygen (O2) through the following pair of reactions:

O2 + hν → O + O

O + O2 → O3

where hν represents the energy of a photon of ultraviolet light with a wavelength less than 260 nm.

Ozone is also dissociated by short-wavelength ultraviolet light (200-300 nm) through the reaction:

O3 + hν → O2 + O.

The oxygen atom formed from this reaction may recombine with molecular oxygen to regenerate ozone, thereby
completing the ozone cycle. The great importance of stratospheric ozone is that it absorbs harmful short-wavelength
ultraviolet light before it reaches the Earth's surface, thus serving as a protective shield.

In recent years, the effect of chlorofluorocarbons, commonly known as Freons or CFCs, on the ozone cycle has
become of great concern. CFCs rise into the stratosphere where they are dissociated by ultraviolet light, producing
chlorine atoms (Cl) through the reaction:

CFC + hν → Cl + CFC (minus one Cl).

These chlorine atoms react with ozone to produce ClO and molecular oxygen: Cl + O 3 → ClO + O2.

ClO reacts with the oxygen atoms produced from the photodissociation of ozone in above ozone equations to
produce molecular oxygen and a chlorine atom: ClO + O → O2 + Cl.

Therefore, the presence of CFCs interrupts the natural ozone cycle by consuming the oxygen atoms that should
combine with molecular oxygen to regenerate ozone. The net result is that ozone is removed from the stratosphere
while the chlorine atoms are regenerated in a catalytic process to continue the destructive cycle.

ii. Photofragmentation, e.g., the side chain of riboflavin can split off to form lumiflavin.
 Isomerization
A photochemical reaction occurs when internal conversion and relaxation of an excited state leads to a ground state
isomer of the initial substrate molecule, or when an excited state undergoes an intermolecular addition to another
reactant molecule in the ground state.

For example;

i. Cis-Trans Isomerizations,
-When irradiated with uv-light olefins usually undergo cis-trans isomerization.
-The transformation can be carried out either by direct irradiation of the olefins or by sensitized irradiation.
-It may either occur through a singlet or a triplet excited species.
-It has been reported that isomerization in the triplet state has a lower barrier to rotation around the carbon-carbon
bond.
e.g., all-trans retinal can be converted to 11-cis retinal.
 ii. Photosensitized Isomerization of the trans, trans Dienes by the Triplet under Illumination

iii. Photoisomerization of Stilbene

Direct irradiation of solutions of either cis or trans-stilbene gives rise to a constant mixture having 93 % cis-stilbene
and 7 % trans-stilbene.

Photoionization
The gas-phase photoionization (removal of an electron) also belongs to dissociation reactions. The reactions below
may occur in the upper atmosphere due to short-wavelength UV radiation from the Sun.

Cleavage or Norrish Type I reaction

An important primary photoprocess of carbonyl compounds is cleavage, also known as a Norrish Type I
reaction.

The Norrish type I reaction is the photochemical cleavage or homolysis of aldehydes and ketones into two free
radical [Link] recombination, the acyl and the alkyl radicals formed in the primary reaction can
undergo numerous secondary reactions that are responsible for the multitude of final products.
 Photorearrangement

Rearrangements of electronically excited molecules follow reaction pathways that are usually inaccessible for the
ground state (activation barriers in the ground state are very high).

i. . e.g., 7-dehydrocholesterol can be converted to vitamin D3.

ii. Photoinduced rearrangements of stilbene that has been extensively studied. The cis-trans isomerization of
double bonds belongs to such reactions. In addition to double bond isomerization, cis-stilbene undergoes also
cyclization with a lower quantum yield to form dihydrophenanthrene. The cis-trans isomerization of stilbene
occurs through rotation around the double bond. In the ground state this rotation encounters a large barrier, i.e.,
there is a maximum on the ground-state potential energy surface at the geometry corresponding to a twist angle
of about 90o. In contrast, both the first singlet excited state and triplet state have a minimum approximately at
the same geometry. The close proximity of the minimum and maximum facilitates a jump to the ground state .
The cis-transisomerization of azobenzene may proceeds not only through rotation, but also through nitrogen
inversion, i.e. in-plane motion of the phenyl ring.

iii. Two illuminating examples of photoinduced rearrangements of substituted benzaldehydes. Intramolecular

hydrogen transfer in 2-hydroxybenzaldehyde is an extremely fast reaction in the singlet excited state.
However, the process is completely reversed upon a jump to the ground state. Overall, no chemical conversion
 is observed and excitation energy is either dissipated as heat or emitted as light, but with a longer wavelength.
This behavior is typical for aromatic carbonyl compounds with ortho-hydroxy groups, and they found
application as UV protectors, in sunscreens for example. Molecules acting as UV protectors absorb light that is
harmful for biological molecules, and convert light into heat or radiation that is biologically benign. In
contrast, an intramolecular hydrogen transfer in 2-nitrobenzaldehyde initiates a sequence of the ground-state
reactions that leads to 2-nitrosobenzoic acid. The latter molecule is a moderately strong acid, and dissociates in
aqueous solutions so that the photochemistry of 2-nitrobenzaldehyde can be used to create a rapid pH-jump in
solution. Many biological macromolecules, such as proteins and nucleic acids, show pH-dependent
conformational changes. Those changes can be monitored in real time by using the light-induced
pH-jump.

Charge-transfer reactions
Norrish Type II reaction process
Norrish Type II reaction process is Intramolecular abstraction of a -hydrogen. A proton or an electron is abstracted
from the excited molecule by the ground-state species. These processes, often combined under the term "charge-
transfer reactions", play an important role in many photoinduced processes.
Hydrogen atom abstraction reactions are known for more than 100 years and belong to the most extensively studied
photoprocesses. Example; The reaction of benzophenone in the triplet excited state with isopropanol (as below
equation). The dimethylketyl radical produced transfers a hydrogen atom to benzophenone in the ground state to
produce another diphenylketyl radical. It is interesting that only one photon is needed to convert two molecules of
the reactant and the quantum yield of benzophenone decomposition has a limiting value of 2.

Intramolecular hydrogen abstraction is a common photoreaction of carbonyl compounds with a hydrogen atom
attached to the fourth carbon atom. The resulting diradical can form cycloalkanol or undergo C-C bond fission to
give an alkene and enol. The latter is usually thermodynamically unfavorable and converts to a ketone.
Photosubstitution
Photosubstitution reactions are well characterized for substituted aromatic compounds. An illustrative example is the
photoreaction of m-nitroanisole with cyanide ion. The mechanism involves a complex of the aromatic molecule in
the triplet state with the nucleophile.

Photohydrolysis
A photohydrolysis reaction in aqueous solution (substitution with OH -) was utilized to provide the rapid light-
controlled release of biologically active molecules, such as aminoacids, nucleotides, etc. Biologically inert
compounds affording such release upon photoirradiation are referred to as "caged" compounds. Two-photon
photochemistry is of great interest for such studies, because one can utilize red light or IR radiation, which is not
absorbed by biomolecules, and is biologically benign. The two-photon photohydrolysis of the glutamate ester of
hydroxycoumarin is characterized by a reasonably high cross-section for two-photon absorption.

Photohydration, e.g., uracil can add a molecule of water to it 5-6 double bond when UV irradiated.
Linear addition
Linear addition to an unsaturated molecule, e.g., the pyrimidine base, thymne, in DNA can combine with the amino
acid residue, cysteine, in proteins. This is a model for the photochemical crosslinking of DNA and proteins by UV
radiation

Cycloaddition
Addition reactions are quite common among electronically excited molecules.
Cycloaddition of unsaturated molecules, e.g., two thymines can react to form a ring product, the thymine dimer, an
important class of products formed in DNA by UV radiation.

Photoinitiated cycloaddition reactions are of great importance for understanding the mutagenic effects of UV
radiation. Two major photolesions produced in DNA by UV light are cyclobutane pyrimidine dimers (CPD) and
pyrimidine(6-4)pyrimidone adducts (P64P) (see below). CPD is formed in cycloaddition involving excited thymine
or cytosine and another pyrimidine nucleobase in the ground state. The proposed, but still not proven mechanism for
the P64P formation includes an unstable intermediate with a 4-membered ring, which undergoes fast H-transfer and
ring opening.

Photooxidation, e.g., the ring structure of cholesterol can add a peroxy group.

Energy transfer
All photosensitized [Link] addition of singlet oxygen to double bonds is well known. Because singlet oxygen
can be generated photochemically via energy transfer, the entire reaction sequence, such as shown below, provides
an example of sensitized addition photoreaction.

Factors Determining Outcome of a Photochemical Reaction

1. The chemical nature of the reactant(s)- the electronic structure of the reactant(s).
2. Environmental variables- reaction medium, reaction mixture composition, temperature, isotope effects.
3. Solvent viscosity- In highly viscous or solid solutions the loss of excitation via light emission or
unimolecular non-radiative deactivation is more probable than a chemical modification of the excited
species. Slow diffusion in viscous solutions may prevent self-deactivation of the triplet state via a
bimolecular process called triplet-triplet annihilation and enhance the efficiency of a photoreaction from
 this state. Triplet-triplet annihilation belongs to electronic-energy transfer processes, which may be
classified as quenching of excited states.

APPLICATIONS OF PHOTOCHEMICAL REACTIONS

Applications of photochemical reaction to the synthesis of naturally occurring systems

1. Photosynthesis

It is the most fundamental connection between light and living organisms. Plants dominate the Earth because the can
capture sunlight and convert it into chemical energy through the process of photosynthesis. This conversion of light
energy by photosynthesis yields approximately 100 terawatts of power annually: six times the power consumption of
human civilization! Photosynthesis supports life on the planet, from microbes to humans. The photosynthetic
machinery of plants, algae and cyanobacteria has been characterized in molecular and structural terms, which has
furthered our understanding of how light is converted into energy-rich biomolecules.

Stages of photosynthesis: When chlorophyll a absorbs light energy, an electron gains energy and is 'excited'. The
excited electron is transferred to another molecule (called a primary electron acceptor). The chlorophyll molecule is
oxidized (loss of electron) and has a positive charge. Photoactivation of chlorophyll a results in the splitting of water
molecules and the transfer of energy to ATP and reduced nicotinamide adenine dinucleotide phosphate (NADP).

The chemical reactions involved include:

 condensation reactions - responsible for water molecules splitting out, including phosphorylation (the
addition of a phosphate group to an organic compound)
 oxidation/reduction (redox) reactions involving electron transfer

Photosynthesis is a two stage process.

The Light dependent reactions occur in the grana, and require the direct energy of light to make energy-carrier
molecules that are used in the second process:

 light energy is trapped by chlorophyll to make ATP (photophosphorylation)

 at the same time water is split into oxygen, hydrogen ions and free electrons:

2H2O 4H+ + O2 + 4e- (photolysis)

 the electrons then react with a carrier molecule nicotinamide adenine dinucleotide phosphate (NADP),
changing it from its oxidised state (NADP+) to its reduced state (NADPH):

NADP+ + 2e- + 2H+ NADPH + H+

2. Bioluminescence,
This is a form of chemiluminescence. It is the production and emission of light by a living organism.
Bioluminescence is a "cold light." Cold light means less than 20% of the light generates thermal radiation, or
heat. Bioluminescence occurs widely in marine vertebrates and invertebrates, as well as in some fungi,
microorganisms including some bioluminescent bacteria and terrestrial invertebrates such as fireflies. The
chemical reaction that results in bioluminescence requires two unique chemicals: luciferin and either luciferase
or photoprotein. Luciferin is the compound that actually produces light. In a chemical reaction, luciferin is
called the substrate. The bioluminescent color (yellow in fireflies, greenish in lanternfish) is a result of the
 arrangement of luciferin molecules. Luciferase is an enzyme. An enzyme is a chemical (called a catalyst) that
interacts with a substrate to affect the rate of a chemical reaction. The interaction of the luciferase with oxidized
(oxygen-added) luciferin creates a byproduct, called oxyluciferin. More importantly, the chemical reaction
creates light.
The appearance of bioluminescent light varies greatly, depending on the habitat and organism in which it is
found. Bioluminescence is used by living things to hunt prey, defend against predators, find mates, and execute
other vital activities. This bioluminescence, observed in animals such as jellyfish and fireflies, have similarly
served as archetypical examples linking light and biology where the emitted light requires both protein scaffolds
and environmentally sensitive small molecules within these scaffolds.

3. Vision
It is the ability to interpret the surrounding environment by processing information that is contained in visible
light. White is the combination of all colors; black is the absence of color. In artificial pigmentation, the primary
colors—the three colors which, when mixed, yield the remainder of the shades on the rainbow—are red, blue,
and yellow. Red mixed with blue creates purple, blue mixed with yellow makes green, and red mixed with
yellow yields orange. Black and white is usually created by using natural substances of that color—chalk for
white, for instance, or various oxides for black. For light, on the other hand, blue and red are primary colors, but
the third primary color is green, not yellow. From these three primary colors, all other shades of the visible
spectrum can be made. The mechanism of the human eye responds to the three primary colors of the visible
light spectrum: thus, the eye's retina is equipped with tiny cones that respond to red, blue, and green light. The
cones respond to bright light; other structures called rods respond to dim light, and the pupil regulates the
amount of light that enters the eye.

4. Phototaxis
It is one of the different forms of taxis. It is characterized by the directional movement of a cell in response to
light. The movement may either be towards the source of light (positive phototaxis) or away from the source of
light (negative phototaxis).
A positive phototaxis is exhibited by phototrophic organisms. They move towards the light source to take advantage
of the light energy necessary in photosynthesis. Examples of phototrophic organisms exhibiting phototaxis are the
phytoflaggellates, e.g. Euglena, and photosynthetic bacteria.

5. Photoperiodism
It is the physiological reaction of organisms to the length of day or night. It occurs in plants and animals.
Photoperiodism can also be defined as the developmental responses of plants to the relative lengths of light and
dark periods. They are classified under three groups according to the photoperiods,they are: Short-day plants ,
Long-day plants and Day-neutral [Link] long-day facultative plants
are:Pea,Barley,Lettuce,Wheat etc.;Short-day plants: Marijuana,Cotton,Rice,etc;Day-neutral plants, such
as cucumbers, roses, and tomatoes, do not initiate flowering based on photoperiodism. Instead, they may initiate
flowering after attaining a certain overall developmental stage or age, or in response to alternative
environmental stimuli, such as vernalisation (a period of low temperature)

Applications of photochemical reaction in food preservation

1. UV Radiation -Used to inactivate micro-organisms on the surface of foods and thin films of liquid. UV
light is absorbed by proteins and nucleic acid, in which photochemical changes are produced. It disrupts
DNA molecules, produce lethal mutations and thereby prevent cell replication. Degradation of the bacterial
cell walls also cause the germicidal effect
-Used extensively in disinfection of equipment, glassware, and air.

Applications of photochemical reaction in production of industrial products.

1. Synthesis of vitamin D2 from ergosterol isolated from certain yeasts.
This is photochemical isomerization .they are electrocyclic ring opening in the vitamin D synthesis.
2. Synthesis of cubans which are antiviral agents,
3. Industrial synthesis of caprolactum, the monomer of nylon 6. This is photochemical isomerization.
Meanwhile, in plastic industry, thermo-reversible hydrogen shift is the main absorber used to protect
plastics from ultraviolet degradation.
4. Manufacture of cleaning solvents, insecticides, and halogenated aromatics (used as synthetic
intermediates) by photochlorination. The development of optical brightener or bleaches made by
one of the primary photochemical processes called luminescence.
5. Synthesis of antioxidants by photosulponation.
6. Development of Film- In the development of film, the photochemistry reaction allows the images
developed from a film to obtain its colors.
7. Reversible Photochemical Reaction in Cosmetics. Chemical substances in cosmetics are mostly
unstable to the light. Photosensitization can occur in cosmetics which are caused by a reaction with
the light. This condition is not good as photosensitization can harm skin. To eliminate this reaction, we
need to remove the unwanted photochemical energy by simply creating the reversible of
photochemical reaction.
8. Laser technology. Lasers are intense sourses of monochromatic and coherent radiation.
9. Fluorescent Dyes -The basic principal of fluorescent dyes is that a short-wave light is converted into
long wave fluorescent light in the visible spectrum. These dyes are responsible to create luminous
colors in advertising, shock colors in fashion up to warning colors in traffic. This fluorescent dye can
emit twice as much light at the longer wavelengths.
10. Fluorescent also used in developing color of television. The green, blue and red fluorescent pigments
are used for it. For automatic sorting of letters and postcards, fluorescent is also involved. Another
application is in marking dials and light switches

Applications of photochemical reaction in production of health care products.

1. Medical imaging- is the process of creating visual representations of the interior of a body for further
medical analysis. Such imaging is generally used in medical fields such as neuroscience, cardiology,
psychiatry, and psychology, amongst others. Common applications include CT (computed
tomography) scans, MRIs (magnetic resonance imaging), ultrasounds, and X-rays (a form of
radiography).
2. Surgical procedures- Lasers are especially crucial in dermatology (skin), ophthalmology (eyes), and
dentistry due to their precision and high power density. Lasers are now widely used for common
procedures such as tumor, tattoo, hair, and birthmark removal. Eye surgery and other surgical
procedures now also use the power of lasers rather than invasive methods of the past.
3. Diagnoses- light applications, specifically lasers have been used in medical diagnosis due to their non-
invasive properties. Routine diagnostics such as tissue oxygenation, early detection of tumors by
fluorescence, and early detection of dental cavities are all performed by laser-based medical apparatus.
4. Photodynamic therapy (PDT) in oncology- PDT is a treatment modality using photosensitizer and
light and the subsequent photochemical reactions to kill cancer cells. PDT has been developed as an
alternative cancer treatment for more than 40 years and is the most well known and established
biomedical application of photochemistry.
5. Gene regulation study in molecular biology- Photochemical crosslinking has been used as a
powerful method for studying protein–nucleic acid interactions in the field of molecular biology. Rapid
fixation or freezing of the specific binding between proteins and gene sequences at specific binding
sites can be aided by photochemical crosslinking using light source dominated by UV, including
inexpensive germicidal lamps and pulsed UV lasers.
6. Photochemical tissue bonding in biosurgery- Photochemical tissue bonding (PTB) focuses on the
surgical modalities of tissue repair, aiming to bond tissue edges or surfaces together. PTB shares the
same mechanism with PDT because of the similarity in tissue–light interactions and the same
photosensitizer systems used such as xanthenes.