Photochemistry

313 C
 Assistant Prof. Abdelreheem A. Saddik
Doctor of Materials Science
Dep. Chem., Fac. of Sc., Assiut University

Office: Chemistry Building (B), 1st Floor,

Room No.104
 The Fate of Excited Molecules
Physical Processes: (Jablonski Diagram):
• When a molecule has been
photochemically promoted to an excited
state, it does not remain for long.
Most promotions are from So→S1.

• Promotions to S2 or S3 etc.. takes place

but usually drops very rapidly to S1 state
(~10-11 - 10-13 Sec.), by collisions with
neighboring molecules (energy cascade).
• Similarly, the initial excitation and the
decay from higher singlet states initially
populates many of the vibrational levels of
S1, but these also cascade, down to the
lowest vibrational levels of S1. Therefore,
it’s in most cases the only important exited
singlet state.

• This state (lowest vibrational level of S1)

could undergo various physical or
chemical processes as shown in a
modified Jablonski diagram as follows:
Figure 4: Modified Jablonski diagram showing transitions
between exited states and the ground state Radiative processes
are shown by straight lines radiationless processes by wavy
lines, IC = internal conversion, ISC = intersystem crossing,
VC = vibrational cascade, hνf = fluorescence,
hνP = phosphorescence.
back
Jablonski Diagram
1. Absorption.
2. Fluorescence.

3. Phosphorescence.
4. Vibrational relaxation.

5. Intersystem crossing.
6. Internal conversion.
 Very Important
Table 4: Physical processes undergone by excited molecules.
Excited states higher than S1 or T, are omitted.

S0 + h S1
Excitation (Absorption)
Vibrational relaxation
S1u S1 + heat
Fluorescence
S1 S0 + h Internal conversion
S1 S0 + heat Intersystem crossing
Vibrational relaxation
S1 T1u
Phosphorescence
T1u T1 + heat
Intersystem crossing
T1 S0 + h

T S + heat
Singlet-singlet
Transfer (photosensitization)
S1 + A (S0) S0 + A (S1)

T1 + A (S0) S0 + A (T1) Triplet-triplet transfer

(photosensitization)
 1 – Internal conversion (ic)

- A molecule in the S1 state can cascade

through the vibrational levels of So and thus
returns to the GS by giving up the energy in
small increments to the environment, it is a
quite slow process because the amount of
energy is large, (nonradiative transitions
represented by wavy arrows).
- Because it is slow, most molecules in S1
adopt other pathways.
 2- Vibrational Cascade,
vc,
(Vibrational Relaxation)

It is a nonradiational process.
This pathway is resulting from transitions
from higher vibration levels to the lowest
vibrational level (Vo) of the state.
 3 – Intersystem crossing (isc)
- Most molecules in S1 can undergo isc to the
lowest triplet state T1. An important example
is a benzophenone (100% of S1→T1).

- ISC is of course a forbidden pathway since

the angular momentum problem must be
taken care of, but this often takes place by
compensations elsewhere in the system.
- ISC is a nonradiative transition represented
by wavy arrows.
 4– Fluorescence (f)
- A molecule in the S1 state can drop to low
vibrational levels of So all at once by giving
off the energy in the form of light.
- It takes 10-9 sec (relatively slow !!)
S1→So (fluorescence) & S2→So is possible.

- Because of the possibility of fluorescence,

any chemical reactions of the S1 must take
place very fast, or fluorescence will occur
before they can happen.
 5 – Phosphorescence:
A molecule in T1 may return to the So by
giving up the heat (isc) or light. Of course,
the angular momentum difficulty exists
here, so isc and phosphorescence are
very slow (10-3 to 10-1 sec). i.e., T1 states
have a longer lifetime than S1.
6- Luminescence:
Under circumstances where the spin
multiplicity (s or t) of the emitting state
( phosphorescence or fluorescence) is in
doubt due to the mixing of excited
electronic states ( as sometimes happens
in inorganic molecules containing heavy
transition elements), the emission is
referred to as “Luminescence”.
 7- Slow fluorescence:
• It is the third type of emission. It has the
same  as fluorescence but occurs much
more slowly.

• It is caused when a molecule in T1 acquires

thermal energy to raise it to a higher
vibrational level equal in energy to the
lowest S1 level and then crosses to So
 S low
1 S1 S0
S C Fluo

• Slow fluorescence can also be caused by

collision between two triplet molecules in
which an excited singlet is produced.
 8 – Photosensitization:

* A molecule in the excited state (S1 or

T1), if nothing happens to it first, may
transfer its excess energy all at once to
another molecule in the environment.

* i.e. transfer of excess energy of excited

molecule all at once to another one
◼D* + A → D + A* Donor - Acceptor

◼D*T1 + ASo →DSo + A+T1 Triplet- Triplet Transfer

◼ D*S1 + ASo →DSo + A*S1 Singlet- Singlet Transfer

Wigner Spin Conservation Rule:
- The energy transfer is a subject to the
Wigner spin conservation rule, which is a
special case of the law of conservation of
momentum.

- According to the Wigner rule, “ the total

electron spin does not change after energy
transfer”.For example when triplet species
interacts with singlet species, the following
are some allowed possibilities:
 * *
1- + +
Singlet and triplet
D* A D A*

2- + doublet and douplet ( two F. R)

3- + + Triplet and two douplets

4- + + Singlet and two douplets

- The two most important types of photosensitization,

both in accord with the Wigner rule, are:
a triplet excited state generate another triplet
& a singlet generates another singlet.
S→S transfer take place over relatively long
distance, e.g. 40 Ao but triplet transfer normally
requires a collision between the molecules.

Both types of photosensitization can be useful for

creating excited states when they are difficult to
achieve by direct irradiation.

Why T → T transfer is important ?

Why T → T transfer is important ?

1- Difficult to obtain triplet state (or often

impossible) by direct irradiation.

2- Have longer lifetime, i.e. much more

likely than singlet to transfer energy by
photosensitization
 Detection of Photosensitization ?

1- If the addition of substance A to the

original substance D quenches the
fluorescence or phosphorescence.

2- If A now exhibits fluorescence or

undergoes reaction which it would not
takes place in the absence of D.
 Efficient Sensitization:

It is most efficient when the excited Donor

(D*)has a higher energy than the excited
Acceptor (A*).
The excess energy appears as kinetic
energy of A* & D.
So, before carrying out photosensitization
one should known the energies of these
states (Table 5).
 Table 5 :Some triplet energies

Compound Energy, Compound Energy,

kcal/mol kcal/mol
Benzene 85 Naphthalene 61
Phenol 82 Nitrobenzene 60
Aniline 77 Chrysene 57
Benzaldehyde 72 Biacetyl 55
Carbazole 70 Benzil 54
Benzophenone 69 Eosin 43
Fluorene 68 Anthracene 42
Quinoline 62 Naphthacene 29
Conversion of Electronic Energy
to Kinetic Energy
It is possible, but relatively rare, for an
excited molecule D* to collide another
molecule A to drop to D (ground state),
without A becoming excited.
The excess energy go into kinetic
energy (trans.., vibr., rot.) of A and D.

D* + A D + A + kinetic energy
 The Chemical Fate of Excited
Molecule:
II- Chemical Processes:

• Both excited singlet and triplet species

can undergo chemical reactions.

• Triplets are more common, because they

have much longer lifetime (10-3-10-1 sec)
than singlets (<10-10 sec).
• Excited singlet species, in most cases,
undergo one of the physical processes
before they have a chance to react
chemically, therefore, photochemistry is
largely the chemistry of triplet state.

• There are many examples of chemical

reactions [Table 6].
 Table 6: Primary photochemical reactions
of an excited molecule (A B C)*

(A-B-C)* → A-B. + C. Simple cleavage into free (1)

radicals
(A-B-C)* → E + F Decomposition into molecules (2)

(A-B-C)* → A-C-B Intramolecular rearrangement (3)

(A-B-C)* → A-B- C Photoisomerizaion (4)
RH Hydrogen-atom abstraction (5)
(A-B-C)*
A-B-C-H +R.
(A-B-C)* → (ABC)2 Photodimerization (6)

(A-B-C)*
( → ABC + A* Photosensitization (7)
 The most common are (1) & (2), and, in the
presence of acceptor A is (7).

• They are either unimolecular reactions (1st

four) or bimolecular.

• Bimolecular reactions are for two excited

molecules.
• Because the concen. of excited molecules is
generally low, reactions are between an
excited molecule and unexcited molecule
either of the same or of another species.
 The above reactions are Primary
processes, Secondary reactions often
follow.

Since the primary products are

frequently Free radicals or Carbenes,
even if they are ordinary molecules,
they are often in the upper vibrational
level and so have excess energy.
The most common photochemical
reaction routes

1. Cleavage into free radicals.

2. Decomposition into molecules.
3. Intramolecular rearrangement.
4. Photoisomrization.
5. Hydrogen atom abstraction.
6. Photodimerzation.
( Table 6 )
 Specific examples on some
Photoreactions :
1) Route 1: [Norrish type I, for ketones]
Simple cleavage to free radicals:
Aldehydes & ketones absorb in the range 230-330
nm region resulting in n→* transition (S→S*)

R h
C R' RC + R' 1ry process
O O
( in case of ketone, this called Norrish type 1
cleavage or type 1 cleavage)

RC R + CO 2ry process
O
Another Examples:

Cl2
h 2Cl
R O O R
h 2R O
R N N R
h 2R + N 2
 2) Route 2: Norrish Type II
Decomposition into molecules:
• Aldehydes (though not generally ketones)

R h
C H RH + CO
O
Norrish type II cleavage
Aldehydes or ketones with -hydrogen undergoes
Intramolecular abstraction of -hydrogen followed by cleavage
of the resulting diradical (see rearrangement ) to give the enol
which tautomerize to aldehyde or ketone and olefin.
3) Route 3:

Intramolecular rearrangement:

CHO COOH

h
NO 2 NO
R R
 4) Route 4:
Isomerizatioin:
Ph Ph Ph H
C C h C C
H H H Ph
Cis- Stilbene Trans -Stilbene
H COOH
HOOC COOH
C C
C C
Ph H
H H
Cinnamic Acid
Maleic Acid

This is because the excited states (S1 or T1) of many olefins

have a perpendicular (instead of planner) geometry.
5) Route 5:
Dimerization and Hydrogen Abstraction
(reduction):
6) Route 6:

Dimerization of cyclopentenone:
O O O O
h
2 +

O
Ground State and Excited States :
◼Electrons can move from the ground
state energy level to a higher one, and
outside energy is required.

◼In photochemical process, this energy is

gained in the form of light.
◼Since the energy levels of a molecule are
quantized, the amount of energy required to
raise the electron in a molecule from one
level to another is a fixed quantity,
i.e. Only light with exactly the frequency
corresponding to this amount will cause the
electron to move to the higher level.

◼If the light of another frequency is sent

through the sample, it will pass out without a
loss in intensity, since the molecule will not
absorb it ( Transparent ).