UNIT-6

ELECTRON SPIN RESONANCE

(ESR) SPECTROSCOPY

Lesson Structure
6.0 Objective

6.1 Introduction

6.2 Principle behind ESR spectroscopy

6.3 Line-width of ESR signal

6.4 Intensity of ESR signals

6.5 Intsrumental Technique in ESR spectroscopy

6.6 Hyperfine structures.

6.7 ESR spectrum of Hydrogen atom

6.8 Selection rules for ESR spectra

6.9 ESR spectrum of one electron system coupled to a

nucleus of spin I = 1

6.10 ESR spectrum due to an unpaired electron coupled to

two magnetic nuclei

 
6.11 ESR spectrum of Methyl Free radical  C H 3 
 


6.12 ESR spectrum of Benzene Anion C6 H 6
–

6.13 Hyperfine splitting rules for predicting the nature of
ESR spectrum
 Electron Spin Resonance (ESR) Spectroscopy)

6.14 Zero-field splitting and fine structure

6.15 Lande splitting Factor(g)

6.16 Factors Affecting g-values

Some solved problems

Model questions

References

6.0 OBJECTIVE

The objective of this chapter is to make the student acquainted with paramagnetic
species such as free radicals, transition metal ions, ions and molecules having odd number
of electrons and their identification using the technique of electron spin resonance (e.s.r.)
spectroscopy.

6.1 INTRODUCTION
Electron spin resonance (ESR), also called electron paramagnetic resonance (EPR),
is a spectroscopic technique confined to the study of species having one or more unpaired
electrons.
Among the large number of systems having one or more unpaired electrons, i.e.
paramagnetic system, the most important ones are free radicals, transition metal ions, ions
and molecules having odd number of electrons.

6.2 PRINCIPLE BEHIND ESR SPECTROSCOPY

1
An electron spins on its own axis and its spin quantum number, s  . The spin
2

motion of an electron gives rise to spin angular momentum, S given by
 h 1
S  S(S  1) , where s 
2 2

11  h 3 h
   1 =
22  2  2 2
This spin angular momentum vector can take only those orientations in the presence

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 Electron Spin Resonance (ESR) Spectroscopy)

of an external magnetic field, in which its components along the direction of the external
magnetic field (along z-axis) are half-integrals.

Z-axis

1 h
+
2 2 3 h
 2 2

 3 h
h 2 2
- 1
2 2

BZ

(Applied magnetic field)

Fig. 6.1. (The two orientations of spin angular momentum
vector in a magnetic field.)

h
The z-component of the spin angular momentum vector is ms . , where ms has a
2

1 1
value of either + ( - spin) or – (   spin). Thus, the spin angular momentum vector
2 2
can take only two orientations in space in the presence of an external magnetic field (BZ).
The orientation angle,  is given by the relation

 h  h
 s( s  1)  cos   ms . ...(6.1)
 2  2

or s( s  1) cos   mS ...(6.2)

The spinning of the electron on its own axis generates a magnetic field and hence an
spinning electron behaves as a tiny bar magnet. The magnetic moment associated with the
spinning electron is given by

 e  h
  g   s  s  1
 2m  2

 eh 
 g   s  s  1
 4m 

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 Electron Spin Resonance (ESR) Spectroscopy)

  g  B s  s  1 ...(6.3)

where ‘g’ is called Lande splitting factor and  B is the basic unit of magnetic moment
of the electron, known as Bohr magneton. The value of g for the free
electron is 2.0023. ‘g’ is a dimensionless constant.

eh
B 
4 m


1.602  10 19

C 6.626  1034 Js 
= 9.2741 × 10–24 JT–1

4  3.14  9.1  10 31
kg 
The negative sign in equation Eq. (6.3). indicates that the spin angular
momentum vector and associated magnetic moment vector orient in opposite
directions.

M agnetic Spin angular

m oment vector m om entum vector

BZ
Fig.6.2: The orientation of magnetic moment vector relative to spin
angular momentum vector.
When a spinning electron is placed in magnetic field ( Z ), the energy of
interaction between the magentic moment vector associated with the spinning
electron and the magnetic field is given by
E    .BZ    cos . BZ
Substituting the value of  from Eq. 6.3, we get.

 
E    g  B s  s  1 cos . BZ  g B BZ S  S  1 cos 

Substituting the value of S  S  1 cos   mS from Eq. 6.2, we get

E  g B BZ mS ...(6.4)

1 1
Since ms has only two values + and – , we have from Eq. 6.4.
2 2

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 Electron Spin Resonance (ESR) Spectroscopy)

1  1
E 1  g  B BZ  mS    ...(6.5)
 2  2
2

1  1
and E 1   g  B BZ  mS    ...(6.6)
 2  2
2

1 1
Here mS   corresponds to lower energy state whereas mS   corresponds to
2 2
higher energy state. It is clear from Eq. 6.5 and Eq. 6.6 that increasing strength of magnetic
E
field increases E 1 while decreases 
1 .
 2
2

+ E + 1 = ½ g B BZ
2 (ms = +½)
E = g B BZ
E
E - 1 = -½ g B BZ
2 (ms = -½)
No BZ
field
Fig. 6.3. Effect of magnetic field strength on the energy of spinning electron.
The difference in energy between the two spin sates of an electron in the
presence of a magnetic field is given by

E  E E
1 1
2 2

1  1 
 g  N BZ    g  N BZ 
2  2 

 g  N BZ ...(6.7)
If electromagnetic radiation of frequency  satisfying the condition.
h  g N BZ ...(6.8)

 1 
is present, transition of electron from lower energy spin state  mS   ,   spin  to
 2 

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 Electron Spin Resonance (ESR) Spectroscopy)

 1 
higher energy spin state  mS   ,   spin  takes place with the absorption of this much
 2 
amount of energy giving rise to ESR spectrum. Eq. 6.8 gives the resonance condition for
ESR spectrum. In a magnetic field of strength 0.34 T, the resonance frequency (  ) is given as
g  N BZ

h

 2.0023   9.274  1024 JT 1   0.34 T 


6.626  10 34 JS
= 9.530 × 109 Hz = 9530 × 106 Hz = 9530 MHz
The frequency falls in the microwave region of electromagnetic spectrum. Hence,
microwave source and techniques have to be applied to record ESR spectra.
Successful observation of the ESR spectrum requires suitable values for the frequency
(  ) and the magnetic field (BZ) to satisfy the Eq. 6.8. For a magnetic field of 0.34 T,  comes
out to be 9530 MHz. Spectrometers operating around this frequency are referred to as X-
band spectrometers. Spectrometers operating at higher magnetic fields (BZ = 1.3 T) with
corresponding higher microwave frequency (  35000 MHz) are also available. They are
called Q-band spectrometers.

6.3 LINE WIDTH OF ESR SIGNAL

The line width of ESR resonance depends on the relaxation time of the spin state
under study. Out of the two possible relaxation processes, the spin-spin relaxation is very
efficient, unless the sample is extremely dilute. The spin-spin relaxation time comes out to
be 10–6 to 10–8 s, much shorter than the spin-spin relaxation time in case of NMR. The spin
lattice relaxation is efficient at room temperature giving relaxation time of about 10–6s, but
becomes progressively less efficient at reduced temperatures. For most samples, therefore
we can choose 10–7s as a typical relaxation time and, using this in Heisenberg’s relation,
h
E  t  , we can calculate a frequency uncertainty (line width) as
2

h 1 1 1
     Hz = 0.796 MHz
4  h t 4t 4  3.14  10 7
An even shorter relaxation time will increase this width, and line width of 10 MHz is
not uncommon. Clearly, it is a much wider spectral line, than in case of NMR, where we
find a normal line width for a liquid to be some 0.1 Hz.
A broad line is more difficult to observe and measure than a sharp line and, for this
reason the ESR signals are recorded as the derivative of the absorption curve with respect to
the magnetic field. An ESR absorption peak and its first derivative with respect to the
magnetic field are shown in Fig. 6.4(a) and Fig. 6.4 (b) respectively.

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 Electron Spin Resonance (ESR) Spectroscopy)

First derivative of
Absorption

BZ

absorption
BZ Width

Fig. 6.4 (a) Fig. 6.4 (b)

The separation between maxima and minima of the derivative curve gives the line
width.

6.4 INTENSITY OF ESR SIGNALS

The energy separation between the two spin states of an electron is much more than
the energy separation between two nuclear spin states. The relative
population of electrons in lower and higher energy spin states is governed by the Boltzman’s
distribution law :

 1
n  
 2   exp  E 
 
 1
n   kT 
 2

Thus, the lower energy spin state is more populated than the upper energy spin state
of the electron. The difference in population between two electronic spin states is larger
than that betw een tw o nucl ear spi n states due to the l ar ge v al ue of E in the former case.
Consequently, the ESR signals are expected to be more intense than the NMR signals.

6.5 INSTRUMENTAL TECHNIQUE IN ESR SPECTROSCOPY

The ESR spectrum like that of NMR can be recorded in two ways. One can either
vary the frequency (  ) across resonance keeping the magnetic field (BZ) constant or the
magnetic field is varied keeping the frequency constant. The latter way is usually preferred
since it is easier to very the magnetic field keeping the stability at very high levels. In ESR
Experiment, it is the magnetic component of the electromagnetic radiation that interacts
with the magnetic dipole associated with the unpaired electron. If the oscillating magnetic
field vector of the radiation is parallel to the applied magnetic field, only an oscillation of
the energy level occurs and not a reorientation of the electron magnetic moment. Transition
between the levels will take place only when there is a reorientation of the electron magnetic

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 Electron Spin Resonance (ESR) Spectroscopy)

moment. Thus, for successful ESR absorption, the oscillating magnetic field of the radiation
must be perpendicular to the applied magnetic field.
The basic components of a X-band ESR spectrometer are :
(a) An electromagnet capable of supplying a homogenous magnetic field
which can be varied linearly on either side of the magnetic field.
(b) Source of microwave radiation in the frequency region of 9.5 GHz.
(c) A suitable sample cavity.
(d) Arrangements for transmitting the radiation energy into the sample
cavity.
(e) Detection system to measure the variation in microwave power.
(f ) A suitable oscilloscope or recorder.

Dummy load

3
Crystal
1 4 detector
Klysteron Preamplifier
2 Microwave
bridge cavity

Phase sensitive
N S detector

To modulating
coils Modulator
Recorder

Fig. 6.5. Block diagram of a simple balanced bridge ESR spectrometer.

Description of the experimental set-up :
A simple block diagram of a balanced bridge ESR spectrometer is given in
Fig. 6.5.
The usual source of microwave radiation is a klysteron oscillator which
produces monochromatic radiation of required frequency. The radiation from the source is
transmitted to the sample cavity through a microwave impedance bridge. The rectangular

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 Electron Spin Resonance (ESR) Spectroscopy)

microwave cavity which contains the sample is kept in between the pole pieces of the
electromagnet. A dummy load is kept in the third arm and a semiconducting crystal in the
fourth arm of the microwave bridge. The radiations that arrive in the fourth arm are detected
by the crystal. It is then amplified and fed to a suitable recorder. Phase sensitive detectors
are usually used to detect ESR signals which are represented as absorption or first derivative
curves. The magnetic field is swept over a small range across the resonance condition by
varying the current in a pair of sweep coils mounted on the cavity walls.
When the bridge is in a balanced position, microwave power flows only in two arms
- the one to the cavity (arm -2) and the other to the dummy load (arm 3). There will not be
any power in the 4th arm. Power in the 4th arm will be there only when the bridge is not
balanced. Thus, if the balance exists, initially no signal appears at the detector and when the
sample absorbs, the balancing of bridge is lost and power appears in the 4th arm resulting
in ESR signals. The width of ESR signals is farely large and hence the spectrum is usually
recorded in the first derivative form which enables us to fix up the frequency position and
estimate the intensity more precisely. Another advantage of derivative from is that it gives a
well defined line width.

6.6 HYPERFINE STRUCTURES

The interaction of magnetic moment of an unpaired electron with those of
neighboring magnetically active nuclei results in the splitting of ESR signals into (2nI+1)
components, where n and I are the number and nuclear spin respectively of magnetic nuclei.
This splitting of ESR signals under the influence of neigbbouring magnetically active nuclei
results in hyperfine structures of ESR signals.
The energy of interaction between the magnetic moment of unpaired
electron and that of a magnetic nucleus depends upon the direction of the
magnetic moment of the electron relative to that of the magnetic nucleus. The
interaction energy is expressed as amSmI,, where ‘a’ is a constant, called hyperfine coupling
constant or hyperfine splitting constant. It is a measure of the extent of interaction between
the magnetic moment of the electron and that of the interacting magnetic nucleus. Now,
the energies of the electronic spin states under the influence of a nearby magnetic nucleus is
given by

Em ,m  g B BZ ms  amS mI ...(6.9)
s I

Thus, for a given value of mS, the energy of electronic spin state also depends upon
the value of mI.

6.7 ESR SPECTRUM OF HYDROGEN ATOM

1 1
Hydrogen atom consists of an unpaired electron (s  ) and a magnetic nucleus ( I  ) .
2 2
The ESR spectrum of hydrogen atom in a solid matrix consists of two peaks of equal intensity

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 Electron Spin Resonance (ESR) Spectroscopy)

centered at g = 2.0023. The two energy levels of a free electron are shown in Fig. 6.6. with
1 1
mS   aligned with the field and mS   aligned opposed to the field. The spectrum of a
2 2
free electron would consists of a single peak corresponding to a transition between the two
energy levels.

1
mS = + 1
2
E 1= + g B B Z
+ 2
2
 E =gB Bz = hv
E
1
E 1= – g B B Z
1 – 2
mS = – 2
2

No field Applied field BZ = 0

BZ = 0

Fig. 6.6. Transition between two spin states of a free electron

(single ESR peak)
However, for each value of electron spin angular momentum quantum number for
1 1
hydrogen nucleus, mI, can have two valves, mI   and mI   giving rise to four different
2 2
energy levels, Fig. 6.7.

1 1
E 1   g B BZ  a
1 ,
2 2
2 4

1 1
E 1   g B BZ  a
1 ,
2 2
2 4

1 1
E 1   g B BZ  a
1 ,
2 2
2 4

1 1
E 1   g B BZ  a
1 ,
2 2
2 4

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 Electron Spin Resonance (ESR) Spectroscopy)

No field
Applied field
(Fig. 6.7)

6.8 SELECTION RULE FOR ESR

The selection rules for ESR transitions are :
mS  1 and mI  0
The two ESR signals for hydrogen atom correspond to the transitions,
E 1 E 1 E 1 E
 1 , 1 , and  1 , 1 ,1
2 2 2 2 2 2 2 2

as shown in Fig. (6.7). For these two allowed transitions,

mS  1 and mI  0
The upfield signal corresponding to the transition,
E 1 1 E 1 1
 ,  ,
2 2 2 2
E 1 1 E 1 1
appears at E1 =  ,  ,
2 2 2 2
1 1  1 1 
  g B BZ  a    g B BZ  a 
2 4  2 4 
1
 g B Bz  a
2

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 Electron Spin Resonance (ESR) Spectroscopy)

The downfield signal corresponding to the transition,

E 1 1 E 1 1
 ,  , appeas at
2 2 2 2

1 1  1 1 
E2   g B BZ  a    g B Bz  a 
2 4  2 4 
1
 g BZ  a
2
Thus, the energy separation between two ESR lines of hydrogen atom is given by
E  E1  E2

1  1 
 g B BZ a   g B Bz  a   g B BZ  1 a  g B BZ  1 a
2  2  2 2
= a (hyperfine coupling constant)

6.9 ESR SPECTRUM OF ONE ELECTRON SYSTEM COUPLED TO A

NUCLEUS OF SPIN, I = 1

We have from Eq. 6.9 : Em ,m I  g B BZ ms  ams mI

s

1
where ms   , and mI  1, 0,  1 ( I  1)
2
mI
+1
0
–1

–1
0
+1

BZ =0 BZ
(no field)
Applied field ( BZ = 0)
Fig. 6.8. Energy levles and allowed transitions for an electron coupled to a nucleus
of spin, I = 1.

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 Electron Spin Resonance (ESR) Spectroscopy)

The energy levels and allowed transitions for an electron spin coupled to a nucleus of
spin, I =1, are shown in Fig. 6.8.
Three transitions of equal intensity, with separation equal to hyperfine coupling
constant (a) are expected. Their energies are :

E1  h1  g B BZ  a

E2  g B BZ and E3  g B BZ  a

6.10 ESR SPECTRUM DUE TO AN UNPAIRED ELECTRON COUPLED TO

TWO MAGNETIC NUCLEI
The energy of spin states of an unpaired electron coupled to two magnetic
nuclei are given by

Em m I ,m I  g B Bz ms  a1ms mI  a2 ms mI ...(6.10)
s, 1 2 1 2

where a1 and a2 are the coupling constants of the electron with nuclei 1 and 2, and
mI , and mI2 are the z-components of the nuclear spin angular momentum for the nuclei 1
1
and 2 respectively.

 1
For the coupling of the unpaired electron with two protons  mI    , each electronic
 2
spin state will split into a quartet as shown below :

1 1 1
E 1 1 1   g B BZ  a1  a2 ...(i)
 , , 2 4 4
2 2 2

1 1 1
E 1 1 1   g B BZ  a1  a2 ...(ii)
 , , 2 4 4
2 2 2

1 1 1
E 1 1 1   g B BZ  a1  a2 ...(iii)
 , , 2 4 4
2 2 2

1 1 1
E 1 1 1   g B BZ  a1  a2 ...(iv)
 , , 2 4 4
2 2 2

1 1 1
E 1 1 1   g B BZ  a1  a2 ...(v)
 , , 2 4 4
2 2 2

1 1 1
E 1 1 1   g B BZ  a1  a2 ...(vi)
 , , 2 4 4
2 2 2

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 Electron Spin Resonance (ESR) Spectroscopy)

1 1 1
E 1 1 1   g B BZ  a1 – a2 ...(vii)
 , ,– 2 4 4
2 2 2

1 1 1
E 1 1 1   g B BZ  a1  a2 ...(viii)
 , , 2 4 4
2 2 2

The energy levels of spin states of an unpaired electron coupled to two protons
and the allowed transitions are shown in Fig. 6.9.

– 1
2
E

BZ= 0 BZ
No field
Applied field (B Z = 0)

Fig. 6.9. Interaction of an unpaired electron with two protons (a1 > a2) .

Following the selection rules, mS  1 and mI  0 , the energies of four ESR signals
observed will be

1 1
E1  g B Bz  a1  a2
2 2

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 Electron Spin Resonance (ESR) Spectroscopy)

1 1
E2  g B Bz  a1  a2
2 2

1 1
E3  g B Bz  a1  a2
2 2

1 1
E4  g B Bz  a1  a2
2 2
If the frequency is kept constant, the four ESR peaks will be observed at the following
fields :

hv a a
BZ   1  2
1
g B 2 g B 2 g B

hv a a
BZ   1  2
2
g B 2 g B 2 g B

hv a a
BZ   1  2
3
g B 2 g B 2 g B

hv a a
BZ   1  2
4
g B 2 g B 2 g B

Here three conditions may arise, based on the relative magnitudes of

a1 and a2.
These are :
(i) a1 > a2 ; Four signals with equal intensity will be observed.
(ii) a1 >> a2 ; Here, interaction due to nucleu 2 may be neglected and two peaks
due to interaction with nucleus 1 are observed at field strengths :

hv a hv a
BZ   1 and BZ   1
1
g B 2 g B 2
g B 2 g B

Each signal will be twice as intense as the corresponding lines when a2 is not
negligible in comparision to a1.
(iii) a1 = a2 ; Here, three ESR signals will be observed at field strengths

hv a
BZ   (a1 = a2 = a)
1
g B g B

hv hv a
BZ  and BZ  
2
g B 3
g B g B

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 Electron Spin Resonance (ESR) Spectroscopy)

The second peak will be twice as intense as the other two peaks, i.e., their
intensity ratio will be 1 : 2 : 1. The interaction of an unpaired electron with two identical
protons (a1 = a2) with allowed ESR transitions is shown in Fig. 6.10.
mI
1

BZ =0 BZ = 0 BZ
(No field) (Applied field)

BZ BZ BZ
1 2 3

BZ

Fig. 6.10. Interaction of an electron spin with nuclear spins of two identical protons.

•
6.11 ESR SPECTRUM OF METHYL FREE RADICAL ( C H 3 )

In methyl free radical, an unpaired electron interacts with three equivalent protons.
• 1
The number of ESR signals expected for C H 3 is equal to four ( 2nI + 1 = 2×3 × + 1 = 4).
2
•
In fact, the experimental ESR spectrum of C H displays four equally spaced signals with
3

•
the intensity ratio 1 : 3 : 3 : 1. The energy of spin states of the unpaired electron in C H
3

coupled with three equivalent protons and allowed ESR transitions are shown in Fig. 6.11.

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 Electron Spin Resonance (ESR) Spectroscopy)

mI
3
mI
2 +1/2
mI
1

1 +1/2
+ –1/2
1 2 +1/2
ms = + +1/2
2 –1/2
+1/2
–1/2
–1/2
–1/2 +1/2
–1/2
–1/2

–1/2
1
-
2
E 1
- +1/2
2
–1/2
–1/2
+1/2
–1/2
1 +1/2
ms = - +1/2
2 +1/2 –1/2
+1/2
BZ = O
(No field) +1/2

BZ = O BZ
(Applied field)
•
Fig.6.11. Interaction of electron spin of C H with nuclear spins of three
3

equivalent protons and allowed ESR transitions.

•
The ESR spectrum of C H 3 is shown in Fig. 6.12.
Intensity

BZ
•
Fig. 6.12. ESR spectrum of C H 3

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 Electron Spin Resonance (ESR) Spectroscopy)

Since the observed spectrum is symmetrical, the proton hyperfine couling

constant is isotropic and the unpaired electron density is distributed equally among the
•
protons in C H 3 . The spacing between the ESR peaks gives hyperfine coupling constant (a)
equal to 22.9 gauss.

• –
6.12 ESR SPECTRUM OF BENZENE ANION  C6 H6 
 

Benzene anion can be formed by the reaction of an alkali metal with benzene in a
solvent such as tetrahydrofuran (THF). Benzene anion results when the alkali metal atom
•
transfers an electron to the benzene molecule. The observed ESR spectrum of C6 H – (Fig.
6

6.13) is symmetrical with seven peaks indiating that the unpaired electron density is
distributed equally among the six protons in the system.

Fig.6.13. ESR spectrum of benzene anion.

As there are six equivalent protons in benzene anion, the expected number of ESR
signals = (2n I + 1)
1
= 2×6× +1 =7
2
Seven lines with intensity ratio
•
–
1 : 6 : 15 : 20 : 15 : 6 : 1, are actually observed in the ESR spectrum of C6 H6 . The
spacing between the lines gives the hyperfine coupling constant (a) of 3.76 gauss.

6.13 HYPERFINE SPLITTING RULES FOR PREDICTING THE NATURE OF

ESR SPECTRUM FOR MORE THAN ONE MAGNETIC NUCLEI
In general an ESR signal is split by n equivalent magnetic nulei of spin I into (2nI + 1)
signals. When the splitting is caused by both a set of n equivalent nuclei of spin In and a set

of m equivalent nuclei of spin I m , the number of ESR lines is given by  2nI n  1  2 mI m  1 .

The following specific cases illustrate the use of these general rules :
(i) When the unpaired electron is delocalized over an non-equivalent protons
1
( I  ) , a spectrum consisting of 2n lines will be observed.
2

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 Electron Spin Resonance (ESR) Spectroscopy)

(ii) When the unpaired electron is delocalised over n equivalent protons, a total of

 1 
(n+1) lines, corresponding to  2n   1  will be observed. Thus, methyl free
 2 

• 
radical  C H 3  , in which the unpaired electron is delocalised over three
 
equivalent protons will give rise to four ESR signals with intensity ratio 1 : 3 :

 • –
3 : 1. Similarly, the benzene anion  C6 H 6  displays seven ESR signals as its
 
unpaired electron is delocalised over six equivalent protons. The intensity ratio
of these signals being 1 : 6 : 15 : 20 : 15 : 6 : 1.
(iii) The intensity ratio of (n + 1) signals arising out of the delocalisation of an
unpaired electron over n equivalent protons is given by the coefficients of the
binomial expression (1 + x)n.
For two protons, n = 2, and
(1 + x)2 = 1 + 2x + x2
Thus, the intensity ratio of three signals will be 1 : 2 : 1.
For three protons, n = 3, and
( 1 + x)3 = 1 + 3x + 3x + x3
So, the intensity ratio of the four signals will be 1 : 3 : 3 : 1.
(iv) If the odd electron is delocalised over two sets of non-equivalent protons, the
number of signals expected is the product of the number expected for each
set, i .e., (2nI n +1) (2m Im + 1)
•
The naphthalene anion , C H – , consists of an unpaired electron
10 8

delocalised over the entire naphthalene ring. It has two different sets,
each of four equivalent protons  and  (Fig. 6.14)

H () H() .-
()H H()

()H H()

H() H()

•
Fig. 6.14 Two sets of H-atoms in C10 H –
8

213
 Electron Spin Resonance (ESR) Spectroscopy)

•  1   1 
Thus, C10 H8– is expected to give  2  4   1  2  4   1  , i.e., 25 ESR
 2   2 
signals. This is found experimentally.
(v) Let us discuss the ESR spectrum of bis - (salicylaldimine copper (II) to
summerise all the points discussed above.
H
H
C=N O

Cu

O N=C

H
H
Bis-(salicylaldimine) copper (II)
Coupling of unpaired electron of Cu(II), a d9 system, with the spin of copper nucleus

 3  3 
 I   results in four main groups of ESR signals  2nI  1  2  1   1  4  . These signals
 2  2 
are further split by two equivalent nitrogen nuclei (I=1) and two equivalent hydrogen nuclei

 1  1 
I   . So, each main group of signals should split into  2  2  1  1  2  2   1  = 5 × 3 =
 2  2 
15 lines. However, the hyperfine structure in each of the four groups consists of eleven
lines of intensity ratio 1 : 2 : 3 : 4 : 5 : 6 : 5 : 4 : 3 : 2 : 1. The eleven lines found for each group
in the actual spectrum result from overlap of some of the fifteen peaks as illustrated in Fig.
6.15.

(a)

(b)
d e f e d

(c)
d 2d d +e 2e e +f 2f f + e 2e e + d 2d d
2×2= 4

2×3 = 6

2×2 = 4

2×1 = 2
2×1=2

1 1+2=3 2+3 =5 3+2=5 2+1=3 1

Fig. 6.15. Interpretation of the ESR spectrum of bis - (salicylaldimine) Cu(II).

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 Electron Spin Resonance (ESR) Spectroscopy)

In Fig. 6.15, (a) represents one of the four main group peaks resulting from the

 3
coupling of unpaired electron spin of Cu(II) with the spin of copper nucleus  I   . The
 2
splitting by two equivalent nitrogen nuclei (I = 1) are indicated in (b) and the subsequent

 1
splitting by two equivalent hydrogen nuclei  I   are indicated in (c). The two nitrogen
 2
nuclei split the peak in (a) into five peaks of relative intensity 1 : 2 : 3 : 2 : 1. These values are
denoted in (b) by d,e and f where the intensities correspond to d=1, e=2 and f=3. The splitting
by two equivalent protons will give rise to three peaks for each line in (b), with an intensity
ratio of 1 : 2 : 1. The intensities indicated by the letters below the lines in (c) result from the
summation of expected intensities. The ratio of intensity of lines in (c) on summation,
comes out to be 1 : 2 : 3 : 4 : 5 : 6 : 5 : 4 : 3 : 2 : 1. The experimental spectrum agrees with this
interpretation.

6.14 ZERO FIELD SPLITTING AND FINE STRUCTURE

When a metal ion is placed in a crystal field, the degeneracy of d-orbitals is lifted by
the electrostatic interactions, but the spin degeneracy remains, until a magnetic field is
applied. However, when the species contains more than one unpaired electrons, the spin
degenracy can also be destroyed by the crystal field. Thus, the spin levels may be split even
in the absence of a magnetic field. This phenomenon is called zero field splitting. For species
with an odd number of unpaired electrons, the spin degeneracy of every level remains
doubly degenerate. This is known as Kramer’s degeneracy. For an even number of unpaired
electrons, the spin degeneracy may be removed completely by the crystal field.
Let us consider the case of a molecule or ion with two unpaired electrons, giving rise
to a total spin of S=1. The two unpaired electrons per molecule or ion forming the triplet
state can be treated for most ESR purposes as a single particle with spin 1. Thus, the angular
momentum vector corresponding to S = 1 is given by :
 h
S  S  S  1
2

h
 1  1  1
2

h h
 1  1  1 = 2  2 units
2 2
In the absence of a magnetic field, this vector orients itself randomly in space. When
a magnetic field is applied, the vector can take up one of the three directions only -with,
across or against the field direction. The components of the angular momentum vector in
the direction of the applied field (BZ) are ms =+1 ,0 and -1. In the applied field, the ms= +1

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 Electron Spin Resonance (ESR) Spectroscopy)

state is raised in energy, the ms= –1 state is lowered and ms = 0 state remains unaffected
(Fig.6.16)

ms = +1

ms = 0

BZ = 0
ms = -1
(No field)
BZ = 0 (Applied field)

Fig. 6.16. Splitting of spin states in a magnetic field.

Applying the selection rule for spin allowed transitions, ms = ±1, only two transitions,
ms =–t to ms = 0 and ms = 0 to ms = +1 are allowed, but both will have identical energy and
hence give rise to only one spectral line. In fact, two spectral lines of different energy are
invariably observed.
Reason for the unsymmetrical splitting of spin energy levels giving rise to two
spectral lines :
Each state with S = 1 is made up of two electrons with parallel spins. We know that
each spin produces a small magnetic field in the vicinity of the other affecting the net field
experienced by its neighbour (dipolar spin spin coupling). Thus, both spins in ms = +1 state
feel an applied field greater than the external field BZ and this state is raised in energy. For
ms=–1, both feel a smaller field, which again raises their energy. In the case of ms=0, the
dipolar field is across the main applied field, hence it is neither raised nor lowered in energy.
Thus, the ms=0 state remains unaffected by the dipolar spin spin coupling.
The net effect of spin spin dipolar interaction is , then to raise both the
ms= +1 and ms=–1 states with respect to ms= 0 state. Thus, the degeneracy of spin state is
lifted due to spin spin dipolar interactions, even in the absence of applied magnetic field.
This splitting of spin states in the absence of applied magnetic field is called zero field splitting
(Fig. 6.17)

ms = ±1

BZ = 0

Fig. 6.17 (zero field splitting)

When a steadily increasing magnetic field is applied, the m s = ±1 levels
diverge, the ms = +1 level is raised in energy while ms = –1 level is lowered (Fig. 6.18)

216
 Electron Spin Resonance (ESR) Spectroscopy)

E
ms = ±1
ms = 0 ms = 0

(zero field splitting) ms=-1

BZ ( = 0)

Fig. 6.18. Zero field splitting and unsymmetrical splitting of spin states
giving rise to two ESR signals.
It is clear that there will be transitions at two different applied fields and the spectrum
will consists of two fine structure lines.

6.15 LANDE SPLITTING FACTOR (G) OR, ELECTRON G-FACTOR

Electron g-factor is the ratio of magnetic moment of the electron to the total spin
angular momentum of the electron. For a free electron the value of g is 2.0023. In many free
radicals, the value of the odd electron is close to that of a free electron, but in metal ions g
values are often quite different from the free electron value.

6.16 FACTORS AFFECTING g VALUES

In general, the magnitude of g depends upon the orientation of the molecule/ion

containing the unpaired electron with respect to the magnetic field applied. In a solution, or
in the gas phase, g is averaged over all orientations because of the free motion of the molecules/
ions. However, in a crystal, the movement of molecules/ions is restricted. If the paramagnetic
radical or ion is located in a perfectly cubic crystal site, i.e., an octahedral or tetrahedral site,
the g-value is independent of the orientation of the crystal and is said to be isotropic. In a
cr ystal si te of l ow er symmetr y, the val ue of g depends upon the orientation of the crystal
and is said to be anisotropic. The z-axis is defined coincident with the highest fold rotation
axis, which can be determined by x-ray crystallography. The gZ value is equivalent to g11,
the g-value obtained when the z-axis is parallel to the external magnetic field. The g-values
along x and y axes are gx and gy, which in a tetragonal site are equal and referred to as g ,
the g-value obtained when external magnetic field is perpendicular to the z-axis. If  be the
angle between the magnetic field and the z-axis, the experimental g-value is given by

g 2  g11
2
cos2   g2 sin2  ...(6.11)

The value of g for an unpaired electron in gaseous atom/molecule/ion for which

Russel Saunders coupling (L-S coupling) is applicable, is given by the expression

217
 Electron Spin Resonance (ESR) Spectroscopy)

J  J  1  S  S  1  L  L  1
g  1 ...(6.12)
J  J  1

1 1
For a free electron, S  , L=0 and J  , the value of g comes out to be 2.0 using Eq.
2 2
(6.12). The actual value of free electron is 2.0023 where the contribution 0.0023 is due to a
relativistic correction. For the halogen atoms in the gas phase, the g value predicted by the
Eq. (6.12) has been found to agree exactly with the experimental value. All halogen atoms

2 1 3
have the same ground state term, P3/2 (L=1, S= , J = ).
2 2

4
Substitution of these values in Eq. (6.12) yields g  , identical with the
3
experimental value. No such agreement is found, however, when the unpaired
electron is placed in a chemical environment, either in a free radical, or in a transition metal
ion complex crystal lattice. In such a chemical environment, the orbital motion of the electron
is strongly perturbed and the orbital degenracy is partly removed or quenched. Jahn Teller
distortions also serve to lift the orbital degenracy. On the other hand, a certain amount of
orbital degenracy tends to be sustained as the result of spin orbit coupling. Thus, complete
removal of orbital degeneracy is prevented by spin orbit coupling but higher fold
degeneracies are often decreased by this effect. Thus, if an electron has orbital angular
momentum, this is maintained by coupling to the spin angular moment, and if it has a spin
angular momentum, this tends to generate orbital angular momentum. Consequently,
because of the quenching and sustaining competition, the orbital degeracy is partly but not
completely removed and a net orbital magnetic moment results, giving rise to a g value
different from the value 2.0023 expected if the orbital degeneracy were completely removed.
In most free radicals, the orbital contributions to the magnetic moment are very
small and the g values are nearly equal to free electron value of 2.0023. The small deviations
(±0.05) often observed for most free radicals are accounted for by the mixing of low lying
excited states with the ground state.
The properties of transition metals are determined to a large extent by the relative
magnitudes of the crystal field and spin-orbit coupling. These two interactions have opposite
effects on orbital degeneracy. Here three cases may be distinguished :
(i) The effect of spin-orbit coupling is much larger than that of the crystal field :
The rare earth ions fall in this class because the f-electrons are deep seated and well
shielded from the crystal field effects so that the spin orbit coupling is not disturbed. So, g
values calculated using Eq. (6.12) for rare earth ions are in good agreement with experimental
values.

(ii) The effect of crystal field is strong enough to destroy the spin-orbit coupling :
The first row transition metals fall in this category. The orbital degeneracy is not

218
 Electron Spin Resonance (ESR) Spectroscopy)

removed completely because of the effect of some spin-orbit coupling. Consequently, a net
orbital magnetic moment results, giving rise to a g value different from the free electron
value. However, g value is closer to the free electron value of 2.0023 than predicted from
Eq. (6.12). Ions having an orbitally non-degenerate ground state such as Fe 3+ (6S) and Mn2+
(6S) have g values nearly equal to the free electron value, since practically there is no orbital
angular momentum. The slight deviation from the free electron value is due to small spin
orbit coupling.

(iii) The effect of crystal field is strong enough to destroy the spin-orbit coupling
completely :
This corresponds to covalent bonding and is applicable to the complexes of 4d and
5d tansition metals and to the strong field complexes of 3d transition metals such as cyanides.

Some Solved Problems

Q.1. Electron spin resonane is observed for hydrogen atom with an instrument operating
at 9.5 GHz. If g value for electron in hydrogen atom is 2.0026, what is the magnetic
field applied ? Bohr magneton,

 B  9.274  1024 JT 1
Soln: Resonance condition for ESR spectrum is

h  g B BZ

h
or BZ 
g B

 6.626  10 Js 9.5  10 S 

34 9 1

= = 0.339 T
 2.0026   9.274  10 JT 
24 1

Q.2. A free electron is placed in a magnetic field of strength 1.3 T. Calculate the resonance
frequency, if g = 2.0023.
Soln: Resonance condition for ESR absorption is

h  g  B BZ ( = resonane frequency)

g B Bz
or 
h

 2.0023   9.274  1024 JT 1  1.3 T 

=
6.626  10 34 JS

or,   3.643  1010 Hz = 36.43 GHz

219
 Electron Spin Resonance (ESR) Spectroscopy)

 3
Q.3. How many ESR peaks would you get for sodium atom  I   ?
 2

 1
Soln: Sodium atom has one unpaired electron  S   . The electron spin will couple with
 2

 3
nuclear spin of sodium  I   to give a hyperfine structure. The number of ESR
 2
peaks
  2nI  1

 3 
  2  1  1 = 4
 2 

3 3 1 1 3 1 1 1
For I  ; mI   ,  ,  , and for S  ; mS   , 
2 2 2 2 2 2 2 2

mI
+3/2
ms = + ½ +1/2

-1/2
-3/2

E
-3/2
-1/2

ms = – ½ +1/2
+3/2

BZ = 0 BZ ( = 0)

Fig. 6.19. ESR spectrum of sodium atom.

Four transitions are allowed according to the selection rule, mS   1 and

mI  0 . Thus, four peaks are observed in the ESR spectrum of sodium atom.
Q.4. Discuss the ESR spectrum of 1, 4-benzosemiquinone (p-benzosemiquinone) radical.
Soln: 1, 4-benzosemiquinone radical is :

220
 Electron Spin Resonance (ESR) Spectroscopy)

H H

O O

H H
Here, the odd electron is delocalised over whole molecule and interacts equally with
the nuclear spins of the four hydrogen atoms. Thus, the four hydrogen nuclei are equivalent
for the odd electron. The number of ESR signals
  2nI  1

 1 
  2  4   1 = 5
 2 
1, 4-benzosemiquinone radical displays five ESR signals of relative intensity 1 : 4 :
6 : 4 : 1.
1
Total nuclear spin for four hydrogen nuclei = 4  2.
2
The resultant nuclear spin, I =2, will have five orientations in an applied field
corresponding to mI = + 2, +1, 0, –1, – 2. The resultant nuclear spin will couple with the
odd electron spin to give a hyperfine structure consisting of five signals.
mI

+2
+1
m s=+½
0
-1
-2

-2
E
-1
0

m s=–½ +1
+2

BZ = 0
(B Z ( = 0)

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 Electron Spin Resonance (ESR) Spectroscopy)

Q.5. Predict the ESR spectrum of the following radicals :

• •
(a) CF2 H (b) 13
CF2 H

Soln: (a) Coupling of the odd electron spin with the nuclear spin of proton splits the
ESR peak into a doublet. Further interaction with the nuclear spin of the two

 1
equivalent fluorine  I   atoms splits each line of the doublet into a triplet
 2
with intensity ratio 1 : 2 : 1. Hence, the total numbers of ESR signals expected
•
for CF H is six. Total number of ESR signals can also be calculated by using
2

the expression

 2nIn  1  2m Im  1

 1   1 
  2  1  1  2  2   1
 2   2 

=2×3 =6
Here, n = no. of H-atoms,
In = nuclear spin of proton.
m = no. of F-atoms,
Im = Nuclear spin of F.

•
(b) In 13CF H , all the three nuclei, i.e., 1H, 19F and 13Care magnetic each of nuclear
2

1
spin, I  . So, the spin of the odd electron will couple with all the three types
2
of magnetic nuclei to give a hyperfine structure. The number of signals in the
•
hyperfine structure of 13CF H .
2

 1   1  1 
  2  1   1  2  2   1  2  1   1
 2   2  2 

= 2 × 3 × 2 = 12

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 Electron Spin Resonance (ESR) Spectroscopy)

Model Questions
Q.1. Discuss the principle behind ESR spectroscopy. What type of species are studied by
this technique ?
Q.2. What is Lande splitting factor (g) ? What are the factors which affect the value of g ?
Q.3. How do crystal field and spin -orbit coupling affect the value of g ?
Q.4. Why is the line width of ESR signal larger than that of NMR signal ? Why is ESR
signal presented in derivative form ?
Q.5. What is zero field splitting ? Explain with suitable example.
Q.6. Describe the experimental technique for recording ESR spectrum.
Q.7. Discuss the ESR spectrum of the following species :

• •
•–
(a) C H 3 (b) C6 H6 (c) C10 H• – (d) CH F
8 2

•
(e) 13
CH2 F

Q.8. What do you mean by hyperfine structure ? How do they arise in ESR spectra ?

References
1. Fundamentals of molecular spectroscopy : C.N. Banwell and E.M. Mc Cash, 4th
Edition, Tata McGrow-Hill.
2. Physical methods in inorganic chemistry : R.S. Drago, Affiliated East west press private
limited, New Delhi.
3. Molecular structure and spectroscopy : G. Aruldhas, Prentice Hall of India Private
limited, New Delhi.
4. A textbook of physical chemistry (Vol. -4) : K.L. Kapoor, Mac Millan India Limited.



223