7

Electron Spin Resonance (ESR)

Spectroscopy

7.1 Introduction
Electron spin resonance (ESR) spectroscopy, invented by Zavoiskii in 1944, is
similar to NMR spectroscopy. ESR spectroscopy is an absorption spectroscopy
which involves the absorption of radiation in the microwave region (10 4 -10 6
MHz) by substances containing one or more unpaired electrons. This absorption
of microwave radiation takes place under the influence of an applied magnetic
field. The substances with one or more unpaired electrons are paramagnetic and
exhibit ESR. Thus, ESR spectroscopy is also called electron paramagnetic
resonance (EPR) spectroscopy or electron magnetic resonance spectroscopy.
Substauces containing unpaired electrons, i.e. paramagnetic substances are of
two types:

(i) Stahle Paramaguetic Substauces

These include simple molecules like NO, 0 2 and N0 2, and the ions of transition
metals and their complexes, e.g. Fe3+, [Fe(CN) 6] 3- etc. Such stable paramagnetic
substances can be easily studied by ESR spectroscopy.

(ii) Uustable Paramaguetic Substauces

Theseare generally calledfree radicals or radical ions and are formed either as
intermediates in chemical reactions or by irradiation of a stable molecule with
UV or X-ray radiation or with a beam of nuclear particles. If the lifetimes of
such radicals is greater than 10-6 s, they may be studied by ESR spectroscopy.
Paramagnetic substances with lifetimes shorter than w-6 S, may also be studied
by ESR spectroscopy if they are produced at low temperatures in the solid state,
called matrix technique, as this increases their lifetimes. ESR spectroscopy is
most useful in the study of free radicals.

7.2 Theory
The principle ofESR is similar to NMR, except that electron spin is involved in
ESR instead of nuclear spin which is involved in NMR. An unpaired electron,
like a proton, has a spin and this spin has an associated magnetic moment. An
±
electron of spin s = can have the spin angular momentum quantum number

L. D. S. Yadav, Organic Spectroscopy

© Springer Science+Business Media Dordrecht 2005
 Electron Spin Resonance ( ESR) Spectroscopy + 225
values of ms = ± t. In the absence of an applied magnetic field, the two values
t t
of ms, i.e. + and- will give rise to a doubly degenerate spin energy state. *
When a magnetic field is applied, this degeneracy disappears and two non-
degenerate spin energy states result. The low energy state (more stable) has the
spin magnetic moment aligned with the applied magnetic field and corresponds
to the quantum number ms = - t,
whereas the high energy state (less stable),
ms = + t, has its spin magnetic moment aligned against the applied field. These
energy states are illustrated in Fig. 7 .1. These two states will possess energies
that are split up from the original state with no applied magnetic field by the
amount -J-LeHo and + J-LeHo for the low energy and high energy states, respectively
(Fig. 7.1). Here f-te is the magnetic moment of the spinning electron and H0 the
applied magnetic field acting on the unpaired electron.

ms=+t

r
No applied field

m,=-t t
Applied field Ho

Fig. 7.1 Energy states of an unpaired electron in an applied magnetic field H 0

In ESR, a transition between the two different electron spin energy states
takes place by absorption of a quantum of radiation of an appropriate frequency
in the microwave region. When the absorption takes place, the following relation
holds good:

(7.1)

where 2J-LeHo is the difference between the two electron spin energy states
(Fig. 7.1), i.e.
lleHo - (-J-LeHo) = 2f-LeHo
Strictly speaking, the relation given in Eq. (7.1) holds good for a free electron.
The energy of transition .1E in substances containing an unpaired electron is
more accurately given by the relation

.1E = hv = gßH0 (7.2)

where h is the Planck's constant, v the frequency in cycles per sec, ß the Bohr

*Two spin energy states having the same energy.