Notes on Photochemistry of Dr.

Bapu R Thorat

Photochemistry
Dr. Bapu R Thorat
Department of Chemistry,
Government of Maharashtra,
Ismail Yusuf Arts, Science and Commerce College, Mumbai
3.1. Introduction
3.2. Thermal and photochemical reactions
3.3. Einstein energy
3.4. Behavior of the Excited State Molecules
3.5. Quantum Yield
3.6. Terms used in photochemistry
3.6.1. Non-Radiative Processes
3.6.1.1. Internal Conversion
3.6.1.2. Intersystem Crossing
3.6.2. Radiative Processes
3.6.2.1. Fluorescence
3.6.2.2. Phosphorescence
3.7. Allowed and forbidden transitions
3.8. Fate of excited molecules
3.9. Photosensitization
3.10. Photochemical reactions
3.10.1. Photoreduction of carbonyl compounds
3.10.2. Photodimerisation of alkenes, conjugated dienes and
aromatic compounds
3.10.3. Photo-Rearrangement reaction - Cis-Trans isomerism
3.10.4. Intramoleculer Photocyclisation
3.10.5. Norrish Type-I and Norrish Type-II Reaction

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Notes on Photochemistry of Dr. Bapu R Thorat

3.1.
Introduction:
Molecules absorb the photon of appropriate energy so that one of its electrons gets excited into
an orbital of higher energy. The energy of the radiation is nearly equal to or greater than the
energy difference between ground state and excited state i.e. in ultraviolet region or visible
region. The resulting molecule in its excited state or alternative excited may take part in the
chemical reaction. The reaction may be intramolecular (rearrangement, dissociation, etc.) or
intermolecular (addition reaction). In some cases the excited molecule may transfer its energy to
another molecule which in terns undergoes reaction.
At room temperature, initially almost all molecules are present in the ground state (vibrational)
So. The excitations occur so rapidly that the nuclei have no time to alter their relative positions
therefore represented by vertical line. It can be reaches to the energy point correspond to the
excess vibrational energy. It is denoted as S1 (excited single state- the state in which the excited
electron and its original partner have opposite spin). This energy is rapidly dissipated through
molecular collision (vibrational cascade) and then one of the five process take place1. Molecule returns to its ground state either by giving its energy as heat or higher energy
level to ground state followed by vibrational cascade or by emitting the radiations
(fluorescence) of low energy than that of absorbed light.
2. A chemical reaction occurs.
3. Excess energy due to excitation is transferred to another molecule by collision so that
original molecule comes to ground state with excitation of another molecule.
4. One of unpaired electron of the excited molecule undergoes an inversion of its spin and
get transferred to its lower energy state as a triplet T1 in which both electrons (ground
state and excited state) has parallel spin. This is called as intersystem conversion (ISC).
5. In special cases excitation leads dissociation of the excited molecule because S1 state is
more energetic than its dissociation energy level.
The triplet state may be return to the ground state with a further spin inversion either by
emitting the radiations (phosphorescence) or giving up energy in the form of heat; it may
carried out the reaction; it may transfer its energy to another molecule which is excited to triplet
state; it may undergoes association.
3.2.
Thermal and photochemical reactions:
Photochemistry is a branch of chemistry concerned with the chemical effects of light (far UV to
IR). Photochemical paths offer the advantage over thermal methods of forming
thermodynamically disfavored products, overcome large activation barriers in a short period of
time, and allow reactivity otherwise inaccessible by thermal methods.
Difference between photochemical reactions and thermochemical reactions are discussed below:
Thermochemical reactions
Photochemical reactions
These reactions involve absorption These reactions involve absorption of light.
or evolution of heat.
They can take place even in The presence of light is the primary requisite for the
absence of light i.e. dark.
reaction to take place.
Temperature has significant effect Temperature has very little effect on the rate of a

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Notes on Photochemistry of Dr. Bapu R Thorat

on the rate of a thermochemical
reaction.
The free energy change G of a
thermochemical reaction is always
negative.
They are accelerated by the
presence of a catalyst.

photochemical reaction. Instead, the intensity of light has a

marked effect on the rate of a photochemical reaction.
The free energy change G of a photochemical reaction
may not be negative.
Some of these are initiated by the presence of a
photosensitizer. However a photosensitizer acts in a
different way than a catalyst.

Photochemical reactions take place on the absorption of radiations (photons) by molecules,

whereas thermal reactions are initiated by the absorption of heat energy, manifested by an
increase of temperature. Thermal reactions differ from photochemical reactions in number of
ways.
Thermal activation takes place by collision between the reactive species with itself or with other
reactants or even with vessel containing the reaction mixture. There is no way of controlling the
energies of the colliding molecules and thermal energy may be distributed among all the modes
of excitation in the species. In a molecule these modes include translational, rotational and
vibrational excitations. The electronic excitation mode can be excited but its population at room
temperature will be negligibly small and can be confirmed from the Boltzmanns distribution, i.
e. if n1 and n2 are the population of the molecules in the ground and first excited singlet state
populated by the 500 nm photon (corresponds to energy commonly used in chemical reactions)
the population ratio in these two non-degenerate states is given by the equation n2 / n1 = exp (-E/RT)
Where, E = Nav h = Nav h c/, where, Nav is Avogadros number, h is Plancks constant and
(or ) is frequency (or wavelength) of the photon.
In a photochemical reaction molecules can be excited electronically, using 500 nm radiation at
room temperature. The concentration of the molecules produced in the excited state depends up
on a number of factors, e. g. intensity of the radiation source and rate of decrease of excited
molecules by many competing processes. Further a particular species can be excited in the
presence of large number of other molecules which do not absorb radiation in the same region.
If this energy is used in the bond rupture of the molecule, the chemical reactions can take place.
In most of the chemical reactions, the activation energy observed in the ground electronic state
is nearly of the same magnitude as used in the electronic excitation process. If it is assumed that
the electronic excitation energy is used partly or completely to overcome the activation energy,
then it may be expected that the electronically excited molecules will react much faster at room
temperature than the molecules in the ground state. Thus the photochemical reactions can be
distinguished from thermal reactions, firstly by relatively large concentrations of highly excited species,
which may react faster than the ground state species and may even participate isothermally in the
processes that are endothermic for the latter and secondly, the electronic excitation may lead to the new
electronic configuration of the molecule (for example cis-trans isomerization).
Thermal reactions take place mainly in the rotationally-vibrationally excited states while
remaining in the ground electronic state. The energy is distributed between molecules

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Notes on Photochemistry of Dr. Bapu R Thorat

according to the Maxwell-Boltzmanns distribution law. In photochemical reaction energy can
be located in any one particular quantum state and hence a particular bond can be broken in a
molecule if it absorbs mono-chromatic radiation of an appropriate frequency. The energy of
absorption is given by the well known Bohrs relation: E = h .
Pyrolysis of complex molecules leads to large number of free radicals and molecular fragments
with Maxwell-Boltzmanns distribution of energies. These free radicals at high temperatures are
highly reactive and short lived and hence have a very low concentration. Photochemically, with
selection of a proper wavelength, a selective bond rupture can be achieved even at low
temperature with large concentrations.
3.3.
Einstein energy:
For any chemical reaction, energy is required in two ways: (i) as energy of activation Eact, and
(ii) as enthalpy or heat of reaction H. The need for energy of activation arises because on close
approach, the charge clouds of the two reacting partners repel each other. The reactants must
have sufficient energy to overcome this energy barrier for fruitful interaction. The enthalpy of
reaction is the net heat change associated with the breaking and making of bonds leading to
reaction products. In thermal or dark reactions, the energy of activation is supplied as heat
energy. In photochemical reactions, the energy barrier is by passed due to electronic excitation
and one of the products may appear in the excited state.
The bond dissociation energy per mole for most of the molecules lie between 150 kJ and 600 kJ.
These energies are available from Avogadros number of photons of wavelengths lying between
800 nm and 200 nm respectively, which correspond to the visible and near ultraviolet regions of
the electromagnetic spectrum. The same range of energies is required for electronic transitions
in most atoms and molecules. From Bohrs relationship, the energy equivalent of a photon
(Einstein - An Avogadro number of photons is called an einstein) of this wavelength is
calculated as
E = E2 E1 = h
Where, h = Plancks constant and is the frequency of absorbed radiation. When expressed in
wave number (

) in reciprocal centimeter (cm1) or wavelength (

) in

nanometer (nm) and substituting the values for h and c (the velocity of light), we get
.

In this system, the unit of length is a metre (m), the unit of mass is kilogram (kg) and the unit of
time is second (s). All the other units are derived from these fundamental units. The unit of
thermal energy, calorie, is replaced by Joule (1J = 107 erg) to rationalize the definition of thermal
energy.

3.4.

Behavior of the Excited State Molecules:

Depending on the excitation wavelength, the molecule can be raised to one of the several
different vibrational levels of the excited states. The various ways in which this excited molecule
can behave are shown in following Figure, known as Jablonski diagram. These processes can
be broadly divided in to two categories:

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Notes on Photochemistry of Dr. Bapu R Thorat

A. Photophysical Process: In this process the molecule returns to the ground state without
change in the structure of the molecule. This includes non-radiative and radiative
processes.
B. Photochemical Process: The excited molecule decomposes into atoms or radicals and
these intermediates may take part in further reactions. Unlike the above processes, this
process is generally accompanied either with change of mass in the reactants or change
in the molecular structure (for example, isomerization).
a. Primary Process: Primary process is defined as a sequence of steps which starts with the
absorption of radiation and ends up with any of the process mentioned below.
1. Radiative: This involves two kinds of processes. One is fluorescence and the other
phosphorescence.
2. Non-radiative: This process also can be classified into internal conversion and
intersystem crossing.
3. Chemical reactions: This process may directly lead to the products or may decompose
involving intermediates.
4. Quenching.
5. Energy Transfer
The primary process is generally named after the last step. For example if the primary step is
emission of light then the primary step is either fluorescence or phosphorescence. If the last step
is deactivation without emission of radiation, it can be either internal conversion or intersystem
crossing. Similarly several mechanisms for dissociation are recognized and these are classified
as optical dissociation, pre-dissociation, induced predissociation, and so on.
b. Secondary Process: It is quite common that some species formed in the primary steps
further react to form the final products of different chemical nature. Such
transformations are called secondary steps or secondary (thermal) reactions. The most
common example is the formation of free radicals or atoms by dissociation of excited
molecules and their further reactions with other molecules. For example in the
photochemical reaction between chlorine and hydrogen as given below:
Cl2 + h 2 Cl
. (A)

Cl + H2 HCl + H
. (B)
The step (A) is primary step whereas the step (B) is the secondary step. Any further reactions of
hydrogen atom will also be secondary step.

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Notes on Photochemistry of Dr. Bapu R Thorat

Diagram: Jablonski diagram:

3.5. Quantum Yield:

The concept of quantum yield or quantum efficiency was first introduced by Einstein. The
quantum yield or efficiency of a photophysical or photochemical process provides information
about the extent of particular process occurred after excitation. As originally understood, it was
the number of molecules of reactant consumed for each photon of light absorbed. It is denoted by letter
.

..

1
2

Equation (2) can also be stated in terms of moles of reactant and moles of photons. One mole of
photons is called an Einstein, so that

In a chain reaction, can exceed unity, but in a non-chain reaction, 1. Quantum yield
defined by equation (3) is very misleading because the product can be formed in primary as
well as secondary steps, whereas equation (3) does not tell whether the quantum yield is for
primary step or for total reaction. As suggested by Einstein-Stark law that not more than one
molecule is decomposed in the primary step, quantum yield greater than one means that
secondary reactions are also accompanying the primary process. Thus one should consider two
yields separately. As mentioned earlier that chemical reaction is not the only path followed by
the photo-excited molecule, the quantum yield should be defined separately for each process.
Thus: Sum of quantum yields of all the primary processes should be equal to one.

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Notes on Photochemistry of Dr. Bapu R Thorat

3.6.
Terms used in photochemistry:
The ground states of most molecules all electrons are paired; excited states also can have all
electrons paired. Such states with paired electrons are called singlet states. The excited singlet
state (S1), ground singlet state curve (S0).
Excited states also can have unpaired electrons. States with two unpaired electrons are called
triplet states (T) and normally are more stable than the corresponding singlet states because, by
Hund's rule, less inter-electronic repulsion is expected with unpaired than paired electrons.
3.6.1. Non-Radiative Processes:
There are two non-radiative processes by which the excited molecule can lose its excess energy.
3.6.1.1.
Internal Conversion:
Internal conversion (IC) is defined as the process by which the molecules from the higher excited state
cross over to the lower state of the same spin multiplicities (S = 0) through the vibrational coupling.
Internal conversion is generally observed from singlet to singlet states but this process is also
observed from higher triplet to lower triplet. In this process the radiation is not emitted and is
thus called as non-radiative one. It can be achieved by two ways
If the lower vibrational levels of the upper electronic state overlap with higher vibrational levels
of the lower electronic state, there will be a transient thermal equilibrium and this will allow the
transfer of the molecules from the upper electronic state to the lower one. In this overlap the
nuclear configuration of the two states will be the same and the total energy (i.e. sum of the
electronic and the vibrational energy) of the upper state is equal to that of the lower state. Thus
this transformation is also called as horizontal transition.
In some cases there is a small gap (of few vibrational quanta) between the lower vibrational
levels of the upper electronic state and the upper vibrational levels of the lower electronic state.
The excited molecules from the upper electronic state revert to lower electronic state by a
process known as tunneling. Tunneling is observed in many processes like radioactivity, solid
state phenomenon, and electron and proton transfer reactions. The probability of tunneling
decreases as: (i) the difference in energy between the upper vibrational levels of the lower
electronic state and the lower vibrational levels of upper electronic state increases and, (ii) also
as the mass of the particle increases.
The efficiency of internal conversion depends on the difference in energy between the upper
electronic state and the lower electronic state and the vibrational levels associated with each
state. The presence of vibrational levels in both the electronic states is more important as the
overlap of these states leads to internal conversion. If the number of vibrational levels in the
lower electronic state of the molecule is large, then the overlap between the lower vibrational
levels of the upper electronic state and the upper vibrational levels of the lower electronic state
will increase. This will lead to the higher probability of dissipation of the excitation energy and
hence increase in the internal conversion. The molecules which possess flexibility in their
structure possess large degree of vibrational modes and large number of vibrational energy
levels. In other words internal conversion process is predominant in these kinds of molecules.
Thus fluorescence is rarely observed in aliphatic hydrocarbons and similar molecules. On the

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Notes on Photochemistry of Dr. Bapu R Thorat

other hand aromatic hydrocarbons are rigid molecules and thus possess very few vibrational
degrees of freedom as compared to aliphatic hydrocarbons and thus often show fluorescence.
3.6.1.2.
Intersystem Crossing:
Rate of internal conversion is very fast if the gap between the two electronically excited singlet
states is small and the excess excited energy is converted into molecular vibrations. If the gap
between the lowest excited singlet state and the ground state is substantial, then the excited
molecules may lose their excess energy by emitting radiation in the form of fluorescence. But
there is another path by which the excited molecules may lose energy without emitting
radiation, i. e. by another radiationless process called intersystem crossing (ISC). The main
difference between internal conversion and intersystem crossing is that in the former process, S = 0,
whereas in the latter process S 0, i.e. S1 T1, T1 S0 etc.
The electrostatic repulsion between the two electrons is smaller when these possess the parallel
spin than when these electrons are anti-parallel to each other, i.e. electronic repulsion in any
given triplet state is less than that in the singlet state of the same electronic configuration. In
other words energy of the triplet state will be lower than its singlet state and thus will lie below
the excited singlet state. In general there is substantial overlap between the lowest vibrational
energy levels of the lowest excited singlet state and the upper vibrational levels of the triplet
state. On the other hand based on quantum mechanics, there is a finite probability for the
intersystem crossing to occur but it is very small as compared to the process which does not
involve change of spin. It has been found that the probability of spin forbidden vibrational
(intersystem crossing) process to occur is much lower (10 6 times) than the spin allowed
vibrational crossing to take place. This suggests that mean lifetime of the spin forbidden process
is much longer than the spin allowed process.
It has been observed that aromatic hydrocarbons do undergo some degree of intersystem
crossing from the lowest excited singlet state. The rate of this process is increased:
1. In the molecules having lone pair of electrons.
2. If heavy atoms are present in the molecule or in the solvent. The former is known as
internal heavy atom effect and the latter as external heavy atom effect.
3. In transition metal ions.
3.6.2. Radiative Processes:
Similar to non-radiative processes, there are two radiative pathways also by which the excited
molecules can be deactivated to the ground state.
3.6.2.1.
Fluorescence:
One of the processes followed by the excited molecule for deactivation to the ground state is by
emitting radiation. If the excited state has the same spin multiplicity as the ground state then light
emitted during the transition is known as Fluorescence (i.e. S = 0). In general both the states
involved during fluorescence are singlet.
Sodium atom in its ground electronic state (2S1/2) absorbs radiation to give 2P1/2 and 2P3/2 states.
The atoms revert back to ground state with a mean lifetime of 10 -8 s. In this case the exciting and

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Notes on Photochemistry of Dr. Bapu R Thorat

emitting radiation has the same wavelength and this type of fluorescence is called resonance
fluorescence.
In case of molecules, vibrational relaxation is very fast in solution phase. The molecule excited
to state just after absorption of photon loses excess vibrational energy to solvent molecules and
relax to zero vibrational level of the first excited singlet state. This is followed by solvent
interactions to get further stabilization of the excited state. The energy of the thermally excited
relaxed state is thus lower than that of the initial excited state.
As in absorption, the molecules after emission return to the ground state vibrational levels
which are different from which it started emits the radiations of different wavelengths. Similar
to absorption, the emission transition probabilities are different for different vibrational levels
with different intensity of emission transitions in the spectra.
Vibrational relaxation processes in the ground state occur after the emission of radiation they
are also not reflected in the fluorescence spectra. This clearly suggests that fluorescence
spectrum is always red shifted to the absorption spectrum. The red shift or displacement of the
fluorescence spectrum to lower energy is manifested by Stokes shift, which is defined as the
difference between the absorption and fluorescence band maxima. Stokes shift is a function of
(i) vibrational relaxation, (ii) solvent relaxation and (iii) change in the geometry of the molecule
on excitation.
Several absorption bands are observed from the ground state to different excited states of a
molecule, but only one emission band is observed in the fluorescence spectrum even though the
molecule is excited to higher excited state. This is due to the fact that the other processes like
internal conversion and vibrational relaxation are very fast as compared to the lifetime of the
first excited singlet state and thus the emission cannot compete with these non-radiative
processes from higher excited states. In other words the fluorescence generally occurs from the
lowest excited singlet state to the ground state. This led to the formulation of two rules:
1. Kashas rule, i.e. in a complex (aromatic) molecule the emission occurs from the lowest
excited state of a given multiplicity, i.e. from first excited singlet and triplet states.

2. Vavilovs law, i.e. fluorescence quantum efficiency is independent of the excitation

wavelength.
Since the fluorescence occurs generally from the first excited singlet state to the ground
electronic state, the effects of substituents and size of the aromatic systems (i.e. extended

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Notes on Photochemistry of Dr. Bapu R Thorat

conjugation) on the fluorescence band maximum is nearly similar to that on absorption
spectrum. Whereas the substituents (-OH, -NH2, etc., excited state charge donors) or >C=O
(excited state charge acceptor or vacant orbital donors) containing lone pairs of electrons
increases the energy of bonding orbitals more that those of antibonding orbitals, thus again
decreasing the gap between HOMO and LUMO. The fluorescence intensity observed at any one
particular wavelength is related to the number of molecules populated in the excited state.
Fluorescence has many practical applications, including mineralogy, gemology, chemical
sensors, fluorescence labeling, dyes, biological detectors, and, most commonly, fluorescent
lamps. The most striking examples of fluorescence occur when the absorbed radiation is in the
ultraviolet region of the spectrum, and thus invisible and the emitted light are in the visible
region.
3.6.2.2.
Phosphorescence:
Intersystem crossing is generally followed by vibrational relaxation to the zero vibrational level
of triplet state, as observed in the first singlet state. The deactivation of molecule in the triplet
state follows two routes. (i) Nonradiative process to the higher vibrational levels of the ground
state, also known as intersystem crossing. (ii) Similar to fluorescence, deactivation of the
molecules in the triplet state to different vibrational level of the ground state also takes place by
emitting radiation. Unlike fluorescence, states involved in the emission process in this case are of
different spin multiplicity. Generally this emission is related to triplet singlet but
phosphorescence in general, can be related to emission between any two electronic states of
different spin multiplicity, for example, doublet to singlet etc. Similar to fluorescence,
phosphorescence also leads to different vibrational levels of the ground state. Thus the structure
of the phosphorescence band represents the vibrational structure of the ground state. The gap
between the peaks of the phosphorescence spectrum gives the vibrational frequencies of the
phosphorescing molecules in their ground states and these frequencies match with the
vibrational frequencies obtained with the help of infrared or Raman spectrum. Phosphorescent
substances have the ability to store up light and release it gradually.
3.7.
Allowed and forbidden transitions:
When an electron is excited, it usually goes into the lowest available vacant orbital. For typical
organic molecules, there are 4 possible type of electron excitation:
1) * : Common for alkanes or things that do not have lone pairs or bonds.
2) n * : Common for amines, alcohols, ethers or things that have lone pairs but not
bonds.
3) * : Common for alkenes, aldehydes, carboxylic acids, esters, or things that have
bonds.
4) n * : Common for aldehydes, ketones, esters, things that have lone pairs and
bonds.
The last two are by far the most important in organic photochemistry. These transitions are
arranged according to their decreasing order of energy
* > n * > * > n *.

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Most common examples are Alkenes undergoing *, and carbonyl compounds undergoing
* or n *.
Selection rules tell us that when the transition moment integral is zero then a process is
forbidden. If it is not equal to zero, it is allowed. For electrons to move from one orbital to
another, then their wavefunctions must overlap. The more the wavefunctions overlap, the more
allowed the process is. So we can explain why * is very allowed (large ), and n * less
allowed (smaller ).

The and * are in the same plane, and same areas in space, therefore overlapping
wavefunctions. The lone pairs are perpendicular to the system, and have little overlap with *
and so smaller .
When molecule in gaseous phase undergoes photochemical excitation, then it not remains in its
excited state for long, lowest vibrational level of S1 and then to triplet state if this transition is
allowed i.e. energy gap is comparable. Five different paths available for this excited molecule to
get stabilized to normal state.

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Notes on Photochemistry of Dr. Bapu R Thorat

1. It can cascade down through the vibration levels of the S0 state, and thus retain to the
ground state if no chemical change possible. This process is called as Internal
conversion. It is usually slow process. It is example of radiationless transition of nonradiative decay.
2. The molecule in the S1 state can drop to some low vibrational level of the S0 state by
giving off the energy in the form of light (Radiative transition). This is a relatively slow
process (10-9 secs). This is called fluorescence (same spin multiplicity i.e. S=0). It is more
common in small (diatomic) or rigid (aromatic) molecules. Since the decay is to some low
vibrational level of the S0 state, the h emitted is of lower energy than that which was

put in. i.e. Fluorescence gives out a longer than was used to excite.
3. It is possible for some (but not necessarily all) molecules in the S1 state to undergo an
intersystem crossing (ISC) to the lowest energy triplet state T1. Formally S to T
transitions are forbidden (conservation of angular momentum!), but some are more
forbidden than others! ISC is less forbidden when the S and T states are of similar energy
(their wavefunctions have some overlap). It was more common in carbonyl and/or
aromatic systems and less so in alkene, diene type compounds. ISC occurs without loss
of energy. Since the excited singlet state is higher in energy than the corresponding
triplet state (Hunds Rule), there will be excess energy that has to be given up. The most
common pathway is to ISC to a higher energy T1 state in a vibrational level, and then has
T1 to cascade down to its lowest T1 level. This cascade can be fast (10-12 s).
4. A molecule in the T1 state may return to the S0 state by either emitting: (a) heat (actually
ISC to S0 in a higher vibrational state and then vibrational cascade) or (b) light (this
radiative process is called phosphorescence; different spin multiplicity i.e. S0). Since
both these involve an ISC, they are relatively slow (10-3 to 101 sec) because of their
forbidden-ness. T1 states therefore tend to have longer lifetimes than S1 states.
5. If nothing else initially happens to the excited molecule, then a molecule in its S1 or T1
state can transfer its excess energy to another molecule (photosensitization) or it
undergoes chemical change to other molecule like rearrangement.
Spin selection rule: S = 0
The spin component of the excited state and ground state says that if a transition involves a
change of spin (e.g. singlet to triplet) then the transition is forbidden.
Allowed transitions: singlet singlet or triplet triplet
Forbidden transitions: singlet triplet or triplet singlet
The symmetry component examines the symmetry of the ground and excited state, and
depending on these symmetries the transition will be allowed or forbidden. But these symmetry
calculations are based on a molecule idealised conditions, so the symmetry of the real molecule
may be distorted by the presence of solvent or of a heavy atom on the molecule (the so-called
heavy atom effect we will return to later). Hence if a transition is spin-forbidden, symmetry
allowed, then the probability is very low, and will be <100. But if it is spin-allowed, symmetry
forbidden, then appreciable absorption may be observed (102 104) because of the symmetry
distortions.

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Notes on Photochemistry of Dr. Bapu R Thorat

3.8.
Fate of excited molecules:
The energy gained by a molecule when it absorbs a photon causes an electron to be promoted to
a higher electronic energy level. Excited states may be classified as singlet or triplet based upon
their electron spin angular momentum. The electrons in most non-metallic organic compounds
are paired (opposite spins) in bonding and non-bonding orbitals, resulting in a net zero spin
diamagnetic molecule for the ground state. Such states have a single energy state in an applied
magnetic field, and are called singlets. Electronic states in which two electrons with identical
spin occupy different orbitals (the Pauli Exclusion Principle) have a net spin of 1 (2 x 1/2) and
are paramagnetic. In a magnetic field such states have three energy levels (+1, 0, -1) and are
called triplets. The distinction between singlet and triplet states is important because photon
induced excitation always leads to a state of the same multiplicity, i.e. singlet to singlet or triplet
to triplet. Since most ground states are singlets, this means that the excited states initially
formed by absorption of light must also be singlets. Internal conversion of excited states to
lower energy states of the same multiplicity takes place rapidly with loss of heat energy
(relaxation). Alternatively, an excited state may return to the ground state by emitting a photon
(radiative decay). Conversion of a singlet state to a lower energy triplet state, or vice versa, is
termed intersystem crossing and is slower than internal conversion.
Different chemical
species
A+B

AB + M
+M

Chemical
reaction

Quenching

AB + CD*
Photosensitizatio

Intermolecular
energy transfer

+CD

Dissociation

AB*
excited
molecule

Intramolecular
energy transfer

Ionization

AB+ + e-

Luminescence

hv
AB$

Fragmentation
(free radicals)

AB
S0

Fluoroscence
AB + hv' Phosphorescence

1. A photochemical reaction occurs when internal conversion and relaxation of an excited

state leads to a round state isomer of the initial substrate molecule, or when an excited state
undergoes an intermolecular addition to another reactant molecule in the ground state. The
cis-trans photochemical isomerization of stilbene is a reaction of the first kind. Another
minor product from the photolysis of stilbene has been identified as 1,2,3,4tetraphenylcyclobutane (distilbene), as shown below was the examples of intramolecular
energy transfer.

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Notes on Photochemistry of Dr. Bapu R Thorat

2. The singlet excited state S1 of the molecule or and the triplet state T1 undergoes radiative
decay to ground state S0 is called fluorescence or phosphorescence without any chemical
change in the molecule.
3. The energy state may undergo intersystem crossing and relax in an intramolecular manner.
For example, the S1 (excited singlet) state of naphthalene can convert into the T1 (excited
triplet) state.
4. In the liquid state, the excited state species may be quenched in which the energy of the
excited state species is converted into vibrational energy (heat). Energy is transferred to
another molecule. Usually we observe diffusion controlled dynamic quenching by
collision.
5. The excited state species may fragment to a pair of radicals or, in the case of nitrogen
dioxide to nitric oxide and oxene. Reactions of this type, photolysis, are important in gas
phase and atmospheric chemistry. Many species can be induced to photodissociate. E.g.
Ozone layer deflection by CFC and nitrogen oxides.
6. The photoexcited state may undergo reactions unavailable to the ground state species. For
example, a photoexcited ketone can undergo a 2+2 cycloaddition with an alkene to give an
oxetane (a cyclic ether with a four membered ring), a Paterno-Bchi reaction.
7. The stilbene reactions described above have been occurred through singlet excited states
which convert to transition state through Triplet excited, but the formation of triplet state
by intersystem crossing is not efficient in stilbene. In order to study the behavior of triplet
excited states it is often necessary to generate them by energy transfer from a higher triplet
excited state of a suitable sensitizer molecule. Spin conservation requires that spin
exchange take place during the collisional energy transfer (photosensitization).

Edited by Dr. Bapu R Thorat

Notes on Photochemistry of Dr. Bapu R Thorat

3.9.
Photosensitization:
This is an important alternative to direct excitation of molecules, most commonly used as a way
to create TRIPLET states that are challenging to obtain directly.
For example, Naphthalene has S1 108 kcal/mol above S0, and T1 62 kcal/mol above S0. Notice
here S1 and T1 are very different in energy, so very forbidden Intersystem crossing. Also recall
that we cannot go S to T on direction excitation. The naphthalene can be excited into its T1
excited state by adding a compound (sensitizer), which we can easily irradiate and (1) excite
into S1, which then (2) conveniently can ISC down to a T1 state. This T1 excited state will
conveniently have the right amount of extra energy, which it (3) can unload to the naphthalene
boosting it from S0 to T1. If this causes by the sensitizer then it go from T1 to S0. E.g.
Acetophenone is used as sensitizer having S1 74 kcal/mol above S0, and T1 69 kcal/mol above S0.
O
O
Ph

Ph

108 kcal

S1

triplet state
62 kcal

74 kcal

S1
T1

T1

69 kcal

triplet state
hv

O
0.0 kcal

S0

triplet state

0.0 kcal

S0

3.10. Photochemical reactions:

3.10.1. Photoreduction of carbonyl compounds:
Carbonyl compounds are converted into 1,2-diols and alcohols by irradiation in presence of a
hydrogen donating compounds such as isopropyl alcohol. The reaction occurs in good state
only when the triplet is of the (n, *) type. e.g. reduction of benzophenone and acetone. The
triplet state abstracts hydrogen atom from hydrogen donor/second reactant molecule.
R2C=O

hv

R2 C=O
(S1)

R2 C=O
(T1)

R'H

R2C*-OH + R*'.

The resulting radical either combine2R2C*-OH

R2CH(OH)-CH(OH)R2

The resulting radical abstract hydrogen from solvent.

R2C*-OH + R'H

R2CH-OH + R*'.

The alcohol formation is effective when R radical is stable (tertiary) and the coupling reaction
is dominant when R is the radical stabilizing group. (e.g.-aryl). The coupling reaction is more
effective when the reduced alcohol of the starting carbonyl compound.

Edited by Dr. Bapu R Thorat

Notes on Photochemistry of Dr. Bapu R Thorat

Photoreduction of benzophenone to benzpinacole is carried out by irradiation of a solution
benzophenone and isopropyl alcohol with wavelength 345 nm. The benzophenone forms n *
triplet state at these wavelength but isopropyl alcohol does not shows absorption.
OH
Ph2C=O

H3CCH(OH)CH3

hv, 340 nm
Ph
Ph

Ph
Ph

H3CCOCH3

OH

In addition with isopropyl alcohol, toluene; cyclohexane; methanol are used as solvent.
Ph2C=O

hv

ISC

1
[ Ph2C=O]

[ Ph2C=O]3

The carbonyl n * triplet possess a structure which closely related to the structure of alkoxy
radicals.
R2C---O

RC-----O

Like alkoxy radical, n * triplet abstract the - hydrogen of isopropyl alcohol and forming
two radicals are listed below[ Ph2C=O]3

Ph2C'---OH
(A)

H3CCH(OH)CH3

H3CC'(OH)CH3
(B)

The quantum yield of the benzpinacol formation is one therefore the formation of a second (A)
is not occurred but generated by the reaction between benzophenone and (B).
(B)

Ph2C=O
2(A)

(A)

+ H3CCOCH3
OH Ph
Ph

Ph
Ph

OH

There are certain evidences that explain reduction reaction proceeds through triplet state of
benzophenone isi) The rate of reaction does not decrease appreciably when the reaction is carried out with less
amount of benhydral in benzene. This explains that the excited state of benzophenone is long
lived and waiting for benzhydral molecule.
ii) The presence of small amount of naphthalene in irradiating mixture is reduces the quantum
yield in appreciable manner. The naphthalene does not absorbed the light required for the n
* transition but causes energy transformation so that excited benzophenone molecules
returns to ground state with simultaneously excitation of naphthalene. The naphthalene is
Benzes like quenchers. The triplet benzophenone transfers the energy towards naphthalene.
o-Alkyl substituted aromatic ketones does not under goes photoreduction reaction even
through giving n * triplet because of intramoleculer hydrogen abstraction. The intermediate
enol-tautomer can be trapped by the Diels Alder reaction as-

Edited by Dr. Bapu R Thorat

Notes on Photochemistry of Dr. Bapu R Thorat

R

R
O

hv

CH3

OH

H-transfer
spininversion

COOMe

OH
COOMe

+
[enol-tautomer]

COOMe
COOMe

R
COOMe

-H2O

COOMe

3.10.2. Photodimerisation of alkenes, conjugated dienes and aromatic compounds:

It is reaction of the excited state (singlet or triplet) of one molecule of a reactant with another
molecule of same reactant in ground state forming dimeric product. It forming 1:1 adducts.
Photodimerisation reactions occur in both alkenes and aromatic compounds. Depending on the
structure of the reactant and reaction conditions of the excitation, the excited state is either
singlet or triplet. The isolated olefins absorbs below 200 nm therefore their unsensitized
photodimerization are comparatively little used. The reaction occurs through the singlet excited
state. The photochemical dimerisation reaction is of the 2+2 type explains with the help of
following orbital diagram.
R R

R
2

hv
(2+2)

R R
R R

+
R R

Due to these experimental difficulty, the photoaddition reaction of alkene is carried out through
triplet state of alkene by using photo sensitizer e.g. acetophenone. The max of acetophenone is
270 nm. It first excited to S1 state and then undergoes inter system crossing (ISC) to T 1 state. In
T1 acetophenone, collide with alkene gives ground state sensitizer and triplet alkene. The triplet
state alkene adds through one carbon atom to a carbon atom of a second molecule of alkene and
then undergoes spin inversion followed by coupling gives cyclic product.
hv
acetone

Cyclic olefins are also known to undergo addition reactions instead of dimerisation on
irradiating in methanol. The following reaction has been sensitized by xylene.
H3C
hv
xylene

+ CH3OH

OMe

MeO

CH3

ISC

S1

T1
energy
exchange
on
collision
S0 (PhCOMe)

T1

S0 (alkene)

Edited by Dr. Bapu R Thorat

Notes on Photochemistry of Dr. Bapu R Thorat

Conjugated diene do not undergo photo-dimerization through singlet excited state but
undergoes photocyclisation. The photodimerization of diene (conjugated) has been carried out
by using triplet sensitizer. e.g. Photodimerization of cyclopentadiene in presence of
benzophenone at 330 nm.
Ph2CO

[ Ph2CO]3

hv

Ph2CO

+
H

First two products are formed by [4+2] addition and third by the [2+2] addition reaction.
Three products are formed have nearly equal proportions.
Benzene does not undergo photodimerization but polycyclic aromatic compounds can
undergoes these reactions. e.g. Anthracene dimerises via its excited singlet state [, *] state.
hv

Photochemical dimerization of butadiene is carried out in ether solution in absence of

photosensitizer; two products are formed by intramoleculer cyclisation through excited singlet
state.
hv
Et2O

In presence of sensitizer both (2+2) and (4+2) addition products are formed; either in the ratio
being depends on the sensitizer energy. The data shows that the reaction proceeds through two
non-interconverting excited states. The two conformations of butadiene s-cis and s-trans exists
equilibrium with each other. These two conformations have two non-identical ground states.
Therefore after excitation, two triplet excited states are obtained which are not interconvert with
each other. The s-cis geometry is suitable for the cyclohexene formation however not s-trans.
The excitation energy of s-cis state is slightly lower than that for s-trans. Therefore s-cis excited
state is prefercientialy formed by using low energy sensitizer and hence increased the amount
of cyclohexene derivative. If sensitizer has sufficiently high energy the same ratio of product is
obtained.
hv

S-trans

hv
sensitizer
S-cis

+
cis-

trans-

3.10.3. Photo-Rearrangement reaction:

Some compounds undergo rearrangement reaction in presence of light forming structural
isomers (where groups or atoms in same molecule occupied different positions) or to valence
Edited by Dr. Bapu R Thorat

Notes on Photochemistry of Dr. Bapu R Thorat

bond isomers (where groups or atoms have same positions but having different bonding
framework).
3.10.3.1. Cis-Trans isomerism:
When olefins are irradiated by ultra-violet light, they under goes cis-trans isomerism. This
transformation has been carried out by direct irradiation of olefins or irradiation in presence of
sensitizer. The isomerism has been occurs through singlet or triplet excited state species. The
triplet state has lower barrier to rotation around carbon-carbon bond.
The isomerism has been occurs because bond lost its character in the excited state, here the
two sets of the substitutions tend to occupied mutually perpendicular planes so as to minimize
the repulsive forces between them.
Ph

Ph

hv

Ph

.H

Ph

hv

Ph

Ph

And finally when the molecule come to ground state, it can do so by twisting in either of two
directions to gives cis- and trans- isomers. The final mixture containing cis-isomer as major
isomer because the trans isomer is excited more frequently than cis isomer even though deexcitation gives trans isomers faster. The overall rate of formation of the cis isomer is usually
greater than the trans isomer so that equilibrium constant is greater than one.
The simple olefin absorbs light at 200 nm which is not experimentally convenient therefore
isomerism has been carried out by using triplet sensitizer. e.g. Photoisomerism of stilbene has
been carried out by using benzophenone triplet sensitizer.
hv

Ph2CO
cis-stilbene
trans-stilbene

[Ph CO]1
2

[Ph2CO]3

[ Ph2CO]+ [PhCH=CHPh]3

+[ Ph2CO]3

cis- + trans93%

7%

There are some photochemical cis-trans isomerism has been carried out by using halogens.
Halogen undergoes photochemical decomposition to halogen atom which adds to olefinic
double bond to form radical. Elimination of halogen atom from radical gives raise to constant
ratio of cis and trans isomers.
Br2

.
+ Br

hv
.

2 Br
R H
Br

.R
H

- Br

3.10.4. Intramoleculer Photocyclisation:

Many dienes and polyenes are converted photochemically into cyclic isomers. The reactions are
stereospecific and electrocyclic type when proceeds through singlet excited state. In some
examples the given organic compounds has been converted into highly strained ring
compounds proceeds via triplet sensitized state.
e.g Irradiation of trans, trans-1,4-dimethyl-1,3-buadiene gives cis-3,4-dimethyl cyclobutene by
dis-rotatory ring closer. It explains by orbital symmetry principle.

Edited by Dr. Bapu R Thorat

Notes on Photochemistry of Dr. Bapu R Thorat

hv
H
H

e.g. trans,trans-1,6-dimethyl-2,4,6-hexatriene cyclised with con rotatory motion.

hv

In some examples ring opening reactions are also occurs such asC9H17

C9H17
hv
H

HO

HO

precalciferol

ergosterol

Highly strained compound like bicycle-[210]-pent-2-ene has been photochemically obtained

from cyclopentadiene.
H
H

hv

1,4-Diene are also under goes photochemical rearrangement to vinyl cyclopropane. If diene
containing useless conjugated substituents, reaction proceeds by using triplet sensitizer. It is
called as Zimmermann rearrangement.
hv
sensitizer
O

.
.

spin

OH

OH

Ph

Ph

hv

Ph
Ph

. inversion

Ph

Ph

Ph

Ph

+
Ph

Ph

Ph

Ph

This rearrangement is also called as Di- methane rearrangement. This process involves (1,2)shift. The mechanism and efficiency of the process is depends on the nature of the system. For
acyclic and monocyclic compounds, the rearrangement occurs via singlet transition state. The
rearrangement can involved either singlet or triplet excited state and can be proceeds via
diradical which are formed due to bonding between C2 and C4. The reaction is more efficient
when the substituents are present on the C3 (sp3) carbon atom. The reaction is highly
stereospecific and occurs with retension in configuration at C1 and C5.
hv
sensitizer

.
.

. inversion

3.10.5. Norrish Type-I and Norrish Type-II Reaction:

The bond dissociation energy of a carbon-carbon bond adjacent to a carbonyl group is small and
photo-chemically undergoes hemolytic fission is called Norrish type-I reaction or -cleavage.

Edited by Dr. Bapu R Thorat

Notes on Photochemistry of Dr. Bapu R Thorat

The CO-C bond under goes fission forming alkyl and acyl radical. The acyl radical under goes
decarboxylation followed by recombination of two radicals or abstract of hydrogen atom or
secondary fission to get hydrocarbon and olefin. The carbonyl compound undergoes fission in
gaseous or liquid state through (n *) singlet or triplet state.

CH2

CH2

CH2
hv

CO

CH2

-CO

CO

CH2

(a)

CH2

CH2

CH2

CH2

CH2

CH2

CH2

(b)

(c)

CH2=CH2 + CH3(CH2)n-3CH=CH2

CH3(CH2)n-1CH=CH2

(a) Recombination, (b) abstract of hydrogen, (c) secondary fission.

At room temperature, two acyl radicals undergoes combination to form biacyl and at
temperature above 100oC; acyl radical on decarboxylation to alkyl radical and then
recombination of alkyl radical to get higher alkane.

.+

[CH3-CO-CH3]

CH3-CO-CH3

.
.
CH CO

CH3

CH3CO

CH3CO-COCH3

CH3CO

. +CO

CH3-CH3

CH3

During decomposition more stable radical is formed (alkyl radical). The stability of the alkyl
radicals are- 3o > 2o > 1o > methyl >Ho. The stability of alkyl radical can be important in the
unsymmetrical ketones.
CH3-CO-CH(CH3)2 hv (A)

.CH(CH ) +
3 2

CH3CO

hv (B) (CH ) CHCO

3 2

+ CH3

In above example, the route (a) is currect because of stability of the radical.
O

..

hv

hydrogen
transfer

A ketone having -hydrogen atom is under goes Norrish type-II reaction forming an olefin and
enol of a smaller ketone. It is characterized by the transfer of -hydrogen atom to a carbonyl
group. This transformation has been occurred through six membered transition state forming
methyl carbonyl compound and olefin. Both (n *) singlet and (n *) triplet are participate in
the intramoleculer hydrogen abstraction reaction will the ketone having low lying ( *) state
does not under goes these reaction.
H
O

R1
R2

H
O

hv

O H

R1
R2

+
R

R1
R2
R

R1

CH3

R2

The ,-unsaturated carbonyl compound under goes Norrish Type-II reaction through six
membered transition state to get enol (containing -hydrogen atom) as-

Edited by Dr. Bapu R Thorat

Notes on Photochemistry of Dr. Bapu R Thorat

OH

hv

H3C

OD

CH3OD
H3C

D H

H H
OH

Ph

COOCH3
Ph hv
Type-II

Ph

OH

COOCH3

COOCH3
acid
COOCH3

Ph

+
COOCH3

COOCH3

In many ketones, a Cycloaddition is observed by -hydrogen atom abstraction followed by ring

closer asR

hv

OH

R
or R

H O

R R

OH

H
e.g.

OH

OH

OH

OH
HO

OH

OH

+
O

The Norrish Type-I process is observed in gas phase photolysis while in liquid phase the loss of
carbon monoxide observed with small or intermediate sized ring compounds. But reaction of
type-II is observed in gas and liquid phase. The formation of ketene is observed only in the
transfer of a nucleophilic solvent capable of adding to it e.g. Et2OH, H2O, etc.
For hydrogen abstract process, the hydrogen from -position is taken and forming aldehydes.
These can be explain by taken deuterium instead of hydrogen atom.
O
D
D

..

D
O

.
.

.+ CO
CH2=CH2 +

H
O
H

O
hv
vapour

OHC

. .
CO +

+2 CH2=CH2+

polymer

Edited by Dr. Bapu R Thorat

Notes on Photochemistry of Dr. Bapu R Thorat

O

. .

hv
vapour

CO

.
H

+ CH2=CH2 + CH3CH=CH2

The substituent in the ring of cyclic ketones doesnot affects the photochemical reaction. The
bicyclic ketones loss CO and resulted biradical under goes recombination or hydrogen
abstraction. The use of sensitizer can be altering the product ratios as well as product identify.
e.g. mercury vapour.

.
.

hv
vapour

1)
O

2)

O hv
vapour

..

CO

.
.

CO

polymer

The photochemical reaction is carried out in the presence of mercury vapour which is act as
triplet sensitizer. The additional product is formed as major product. The excited mercury atom
transfer its energy to carbonyl compound for loss of its atomic oxygen and forming new excited
state of very high energy.

..

hv, 2337A
Hg-vapour

The open chain aldehydes and ketones show same photochemical behaviors in gas phase
similar to that of cyclic ketone.
OH
H3C

HO

hv
hv

hv

.
.
CH + CH CO
3

+
H3C

H2C CH2
OH

H3C

.
.

CH3CO
-CO

H3C

hv

CH3CH2CH2 + CH3CO

CH3
OH
CH3
(CH3CH2CH2)2+ CH3COCOCH3

CH3COCH3

The free radical process is obtained by addition of a NO (nitric oxide) which act as good radical
scavenger which trapped the free radical.

Edited by Dr. Bapu R Thorat

Notes on Photochemistry of Dr. Bapu R Thorat

O
H3C

Norrish
+ CH3COCH3 type-II

MeO

OMe

hv
n-Heptane
(liquid)

HO

+ CH3OH

OMe
H

The hydrogen abstraction for the synthesis of ketene is depends on the solvent and steric
requirement. If solvent containing replaceable proton (protic solvent) then react with ketene
forming acid, ester and amide depending on solvent- H2O, alcohol and amines.

..

O
hv
HX

1.

(X= OH/OR/ NR2 )

X
H

2.

hv
CH3OH

OR

OH
O

OR

COOEt

HO

RO

D O O

The formation of aldehyde is occurs in presence of non-protic solvent. Also ring contraction of
cycloketone is occurred by transforming -hydrogen with respect to the carbonyl group and carbon is converted into the CH3 group.
CH2

CH2

(CH2)n

hv

CO

(CH2)(n-1)

CH2

CO

CH
CH3

The three membered ring shows 1,2-shift over carbon skeleton of ketone or aldehyde.
O
1)
O

hv
heat
hv

2)

..

+ CH2=C=O

.. ]

The solvent is also affected the photolysis reaction (solvent is H-transfer agent).
O

OH
hv
RH - R

1.

OH

O O
O2

hv
C6H6

2)
O

O
O

O2

hv

+ CO
O

..

+ CO

. O]

CO2

Edited by Dr. Bapu R Thorat

Notes on Photochemistry of Dr. Bapu R Thorat

In -diradical system, a low energy CO-CO bond is dissociated and forming aldehyde/ketone,
carbon monoxide. The transfer of a hydrogen atom is not a primary process (i.e. absence of
deuterium isotope effect).
O

R1

. .O

R2

R1

CO

R1

R2

+
O

R2

The conjugated unsaturated ketones are photochemicaly extremely active. The fission usually
occurs on the side of the substituents.
O

O
OAc

OAc OAc

HOOC

OAc
O-

OOAc hv

2)

SCOOEt
SCOOEt

hv

. .
. + 2S

O
R

O
CH3
S CH3
O

OH
-AcOH

O
3)

O
O

OAc

4)

OAc

OAc hv
OH2

1)

OAc
O

OEt
O

O
hv
R'OH

O
R

O
R

OR'

It is homologous to Arndt-Eistert reaction.

Ph
Ph
SO2
Ph

hv

SO2

Ph

Edited by Dr. Bapu R Thorat