INDEX:

1.
2.
3.
4.
5.
6.
7.

What is ESR?
Basis of ESR spectroscopy
Energy states of electron
ESR spectrum
Field for resonance
Hyperfine coupling
Hyperfine splitting pattern
(ESR spectra of methyl free radical

and isobutyl free radical)

8. Advantages and Disadvantages.

WHAT IS ESR SPECTROSCOPY?

Electron Spin Resonance Spectroscopy, also referred to
as Electron Paramagnetic Resonance Spectroscopy is a
versatile and non-destructive analytical technique which
can be used for variety of application including oxidation
and reduction processes, reaction kinetics as well as
additional application in biology, medicine and physics.
However, this technique can only be applied to samples
having one or more unpaired electrons.

Spectroscopy is the measurement and interpretation of

the energy difference between atomic or molecular
states. According to Planks Law, electromagnetic
radiation will be absorbed if

E=h
Where E difference in energy of the two states
And h Planks constant
Frequency of the radiation.

The absorption of this energy causes a transition of an

electron from the lower energy state to the higher
energy state.

In ESR spectroscopy, the radiation used is in the

gigahertz range. Unlike most traditional spectroscopy
technique, in ESR spectroscopy the frequency of the
radiation is held constant while the magnetic field is
varied in order to obtain an absorption spectrum

BLOCK DIAGRAM FOR A TYPICAL ESR SPECTROMETER

BASIS OF ESR SPECTROSCOPY

The basis of ESR spectroscopy lies in the spin of an
electron and its associated magnetic moment. When
an electron is placed within an applied magnetic field B0,
the two possible spin state of the electron have
different energies. This energy difference is a result
of the Zeeman Effect.

Zeeman Effect: Its the effect of splitting a spectral

line into several components in the presence of
magnetic field.

The lower energy occurs when the magnetic moment of

the electron, , is aligned with the magnetic field
and higher energy state occurs when the is aligned
against the magnetic field.

The two states are labelled by the projection of

the electron spin, Ms, on the direction of the magnetic
field,
Where Ms =-1/2 is the parallel state
Ms =+1/2 is the anti-parallel state

An unpaired electron can move between the two energy

levels by either absorbing or emitting a photon of
energy h , such that the resonance condition, h =E, is
obeyed.

ENERGY STATES OF THE ELECTRONSo for a molecule with one unpaired electron in a
magnetic field, the energy state of the electron can be
defined as
E = g B B0 M s

= 1/2 g B B0

since Ms =1/2

Where g- the proportionality factor

B- Bohr Magneton
B0- magnetic field
Ms- Electron spin quantum number

From the relationship ie E = g B B0 Ms

There are two important factors to NOTE:
The two spin state have the same energy when
there is no applied magnetic field.
The energy difference between the two spin states
increase linearly with the increasing magnetic field
strength.

ESR SPECTRUM

Like most spectroscopic technique, when the radiation

is absorbed, a spectrum is produced similar to the one
shown above (left).

But in ESR spectrometer, a phase-sensitive detector is

used and this results in the absorption signal being
present as the first derivative as shown above (right).
So the absorption maximum corresponds to the point
where spectrum passes through zero. This is the point
that is used to determine the centre of the signal.

FIELD FOR RESONANCE

We know that, ESR spectrum is obtained by holding the
frequency of radiation constant and varying the
magnetic field tunes the two spins so that their
energy difference is equal to the radiation. This is
known as field for resonance. As spectra can be
obtained at variety of frequencies, the field for
resonance does not provide unique identification of
compound.

The proportionality factor, however, can yield more

useful information.
g = h / BB0
For a free electron, the proportionality factor is
2.00232

For an organic radical, the value is typically quite close

to that of a free electron with values ranging from
1.99-2.01
For transition metal compounds, large variations can
occur due to spin orbit coupling and zero-field splitting,
resulting in values ranging from 1.4-3.0
NOTE: 1. In addition to the applied magnetic field
unpaired electrons are also sensitive to their local
environment.
2.The ESR spectrum of a free radical with one
unpaired electron is the simplest of all forms of
spectroscopy.

HYPERFINE COUPLING:
Since the source of an ESR spectrum is a change in an
electrons spin state, it might be thought that all ESR
spectra for a single electron spin would consist of
just one line. But frequently the nuclei of the atoms in
a molecule or complex have magnetic moment which
produces a local magnetic field at the electron.

This results in the interaction between the electron

and the nuclei. Thus, the interaction of an unpaired
electron by way of its magnetic moment with nearby
nuclear spins results in additional allowed energy
states and in turn multi-lined spectra.

The spacing between the ESR spectral lines indicate

the degree of interaction between the unpaired
electron and the perturbing nuclei. The hyperfine
coupling constant of a nucleus is directly related to the
spectral line spacing and in simplest cases is essentially
the spacing itself.
Thus, in real system, electrons are not normally alone,
but are associated with one or more atoms. There are
several important consequences of this:
(a) An unpaired electron can gain or lose angular
momentum, which can change the value of its
proportionality factor. This is especially
significant for chemical systems with transition
metal ions.

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(b) If an atom with an unpaired electron is

associated, has a non-zero nuclear spins, then its
magnetic moment will affect the electron and,
this leads to the phenomenon of hyperfine
coupling which is similar to J-coupling in NMR,
also this splits the ESR resonance signal into
doublet, triplet and so forth.
(c) The interaction of an unpaired electron with its
environment influence the shape of an ESR
spectral lines. These line shapes can yield
information about like for ex: rate of chemical
reaction.

HYPERFINE SPLITTING PATTERN:

The hyperfine splitting pattern for a radical freely
moving in a solution can be predicted.
(1) For a radical having M equivalent nuclei, each with
spin of l, the number of ESR lines expected is
2Ml + 1.
Example: the methyl radical CH3, has three H (protium)
nuclei each with l =1/2, and the number of lines

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expected is 2M + l.
ie 2(3)(1/2) +1 = 4

Thus 4 lines are expected in the ESR spectrum.and

which is actually observed.

ESR SPECTRUM OF METHYL FREE RADICAL

x-axis : magnectic field
y-axis : first derivative of adsorption.

(2) For a radical having M1 equivalent nuclei each with

l1 and a group of M2 equivalent nuclei,

each with a spin of l2, the number of lines
expected is (2M1l +1)(2M2l + +1)
a spin of

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EXAMPLE: for isobutyl radical the number of ESR lines

expected is
[2(6)(1/2) +1)] [2(3)(1/2) + 1] = 28
Thus 28 lines are expected in its ESR spectra.

ADVANTAGES AND DISADVANTAGES:

Its helps us know the properties of the
electron in the free radical that any
compound have.
PROCESS: During any physical activity like
the bombardment of some huge amount of
energy like light, microwave radiation, or even
heat on say ice (water) some free radicals like
H ,OH, OH2 will be formed and in the process
the ice liquidizes into water. These radicals
sometimes get attached to a location and
when ESR is applied, using a specific
spectroscope the analysis of the cell can be
done.
This is possible because the radiation of the
energy used together with an alternating
magnetic field causes the electrons to move
between their low and high orbits back and

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forth. They start moving faster and faster as

more and more energy is picked up when they
move so. Then the gap between their low and
high orbits becomes smaller as time passes
by. The energy applied gets in between the
gap created and the difference in the energy
levels can be detected by the sensor used for
this purpose.
This application is widely used in the field of
biology and also medicine. There are some
key advantages. The first being it is the
speed with which it can be performed and
yet the analysis of the free radicals is
found to be near perfect. Moreover, the
results of the testing pretty easy to
comprehend and understand. Other
techniques are used to identify free
radicals and also electrons in pairs. This
spectroscopy is used for the purpose of
identification of only free radicals. This is
an important aspect in the study of free
radicals.

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Likewise there are some disadvantages too.

The foremost is that this process should be
performed at low temperature and inly then
desired results can be got. So they are
performed in the specific laboratories where
such temperature can be attained.

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