PRINCIPLES OF PHOTOCHEMISTRY

From electronic spectroscopy of molecules:

• The absorption of a photon by a molecule can raise it to a higher energy

level which may have a minimum in potential energy curve or not.
• According to the Franck–Condon principle, the internuclear distance in the
molecule is not initially changed by the absorption, and the electric dipole
transition moment is proportional to the overlap integral of the initial and
final vibrational states.
• In general, selection rules are obeyed, but the fact is that the actual system
may be more complicated than the ones for which the selection rules were
developed. The selection rule Δ𝑆 = 0 which prohibits transition between
states of different multiplicities (i.e., singlet–triplet), is quite important in
photochemistry.
• When a molecule absorbs a photon it may lose energy through
fluorescence or phosphorescence, but now we will be interested in the fact
that chemical reactions may ensue.
• Electromagnetic radiation in the visible and ultraviolet is generally required
to produce chemical reactions because changes in electronic energy levels
are required.
 Franck-Condon principle,
which states that electronic Electronic excited state
transitions occur in times that
are very short compared to
the time required for the
nuclei to move appreciably.
Transition must occur along
the vertical line ab.

Electronic ground state

the internuclear
distance in the molecule
is not initially changed
by the absorption

∗
Equilibrium bond distance (for 𝑅𝑒 𝑅𝑒
diatomic molecule) in G.S. (Internuclear distance for diatomic molecule)
 the electric dipole transition
moment (𝜇) is proportional to the
overlap integral of the initial and
final vibrational states.

Intensity of a
line ∝ 𝜇2

Internuclear distance
• The first principle of photochemistry, which was stated by Grotthus in 1817 and
Draper in 1843, is that only light that is absorbed can produce photochemical
change.
• The second principle which was proposed by Stark and Einstein from 1908 to
1912, is that a molecule absorbs a single quantum of light in becoming excited:

Thus, a mole of photons can excite a mole of molecules. If the electromagnetic

radiation is extremely intense, as in a laser beam, two photons may be absorbed
essentially simultaneously:
Usually intensity of light of a particular
wavelength is expressed in terms of
energy per unit area per unit time.
• In discussing photochemistry it is convenient to use 𝐼𝑎 to represent the intensity
of light absorbed by a system, expressed as the amount of photons per unit
volume per unit time, where, of course, the amount is expressed in moles.
• A mole of photons is a convenient unit in photochemistry, and it is frequently
referred to as an einstein.
• The intensity 𝐼𝑎 is calculated from the radiant energy of a specific wavelength
absorbed per unit volume per unit time by dividing by 𝑁𝐴 ℎ𝜈.
 Amount of photons
absorbed in 10 min.

Quantum yield:

The rate of a photochemical reaction is proportional to the intensity of light

absorbed , and the proportionality constant is the quantum yield 𝜙.
Thus for the reaction: A + B = 2C

the rate of reaction is given by

From a molecular point of view, the quantum yield is the ratio of the number of
molecules undergoing some sort of change divided by the number of photons
absorbed:

𝐼0 = 1.4 × 10−3 J s −1 ; 𝜆 = 435.8 nm; Intensity absorbed(in Watts)=𝑃𝑎𝑏𝑠

= .801 𝐼0 ; time = 1105 s; Δ Br2 = 7.5 × 10−5 mol L−1 ; volume = 1L.
𝑃𝑎𝑏𝑠 𝜆
𝐼𝑎 = =? 𝑣 = Δ Br2 /time=?; 𝜙 =?
𝑁𝐴 ℎ𝑐 (volume)
Photochemical processes are initiated by the absorption of radiation by at least one
component of a reaction mixture. In a primary process, products are formed directly
from the excited state of a reactant. Examples include fluorescence and the cis–trans
photoisomerization of retinal
Products of a secondary process originate from intermediates that are formed
directly from the excited state of a reactant. Examples include photosynthesis
and photochemical chain reactions.
Competing with the formation of photochemical products is a host of primary
photophysical processes that can deactivate the excited state.
 If there are competing primary processes:

A molecule in an excited state must either decay to the ground state or form a
photochemical product. The sum of primary quantum yields 𝜙𝑖 for all
photophysical and photochemical events i must be equal to 1, regardless of
the number of reactions involving the excited state.
 Jablonski diagram
Excited states and photophysical
transitions between these
states in a "typical" organic
molecule. Radiative transitions
between states are given by
solid lines, radiationless
processes by wavy lines; IC =
internal conversion, ISC =
intersystem crossing . Vertical
wavy lines are vibrational
relaxation processes. Vibrational
and rotational levels are shown
approximately equally spaced
for simplicity in presentation.
 Spin forbidden so is very
slow. It persists even after
excitation radiation is
turned off.

First-order rate constants for the various intramolecular processes.

The wavy lines represent radiationless transitions.
 Under steady illumination the rate equation for each process is given as:

k's are the rate constants, 𝐴10 and 𝐴𝑇𝑆 are the Einstein coefficients for spontaneous
emission. M is intended to represent any atom or molecule that may be present. In
the above mechanism M acts as quencher.