Electron Spin Resonance Spectrometer (ESR)

It was discovery by Zavoisky in 1944.

Electron Spin Resonance Spectroscopy also called electron
paramagnetic resonance spectroscopy [EPR])
ESR has become an essential tool for the study of the structure
and dynamics of molecular systems containing one or more
unpaired electrons.

Electron Spin Resonance Spectrometer (ESR)

ESR spectroscopy is a very powerful and sensitive method for the characterization of the
electronic structures of materials with unpaired electrons.

There is a variety of ESR techniques, each with its own advantages.

In continuous wave ESR (CW-ESR), the sample is subjected to a continuous beam of

microwave irradiation of fixed frequency and the magnetic field is swept.

Different microwave frequencies may be used and they are denoted as S-band (3.5 GHz),
X-band (9.25 GHz), K-band (20 GHz), Q-band (35 GHz) and W-band (95 GHz).

Other techniques, such as electron nuclear double resonance (ENDOR) and electron spin
echo envelope modulation (ESEEM) spectroscopies, record in essence the NMR spectra
of paramagnetic species.

Electron Spin Resonance Spectrometer (ESR)

The theory of ESR spectroscopy shares much in common with that of nuclear magnetic
resonance spectroscopy.

However, the magnetic moment of the electron is about 1000 times as large as the nuclear
moment and the constants employed in NMR theory frequently are different in magnitude
and sign.

Types of Materials Studied by ESR

Inorganic and organic free radicals which possess an odd number of electrons, such as
Fremy's radical

Odd-electron molecules such as NO, N02, and Cl02. Many molecules of this type have
been examined by gas-phase ESR techniques.

Triplet-state molecules, such as O2 and S2. These systems have two unpaired electrons.
Optical irradiation of solids and solutions can often permit investigation of photo excited
triplet states, which are important in photochemistry.

Transition-metal complexes, organometallic compounds, and catalysts containing

metal ions with incomplete 3d, 4d, or 5d electron subshells. The detection of V(IV)
(which has the Is22s22p63s23p63d1 configuration) in crude petroleum is one notable
application of ESR spectroscopy.

Rare earth and actinide compounds containing incomplete 4f, 6d, or 5f subshells.

Impurities in solids, such as semiconductor materials. Odd electrons gained by an

acceptor or lost by a donor impurity may be associated with energy bands in crystals.

Metals. The electrons in conduction bands of metals can be examined by ESR

spectroscopy.

Comparison between EPR and NMR

EPR is fundamentally similar to the more widely familiar method of NMR spectroscopy, with
several important distinctions. While both spectroscopies deal with the interaction of
electromagnetic radiation with magnetic moments of particles, there are many differences
between the two spectroscopies:
1 EPR focuses on the interactions between an external magnetic field and the unpaired
electrons of whatever system it is localized to, as opposed to the nuclei of individual atoms.
2 The electromagnetic radiation used in NMR typically is confined to the radio frequency range
between 300 and 1000MHz, whereas EPR is typically performed using microwaves in the 3 400 GHz range.
3 In EPR, the frequency is typically held constant, while the magnetic field strength is varied.
This is the reverse of how NMR experiments are typically performed, where the magnetic field
is held constant while the radio frequency is varied.
4 Due to the short relaxation times of electron spins in comparison to nuclei, EPR experiments
must often be performed at very low temperatures, often below 10 K, and sometimes as low
as 2 K. This typically requires the use of liquid helium as a coolant.
5 EPR spectroscopy is inherently roughly 1,000 times more sensitive than NMR spectroscopy
due to the higher frequency of electromagnetic radiation used in EPR in comparison to NMR.

(13.2)
/Le = -gf3S
THE RESONANCE CONDITION
The g-value for the free electron, ge, is 2.0023. The approximation made in Equa13.2 is isvalid
for mostparticle
discussions
the ESRmomentum
spectra of the
organic
radicals
Thetion
electron
a charged
withofangular
(orbital
andfree
spin)
and,
and transition-metal
complexesmoment,
whose orbital
angular
it possesses a magnetic
/Le' given
by momentum can be considered
as such,
to be "quenched." Treating the g-value as an experimental quantity does not harm
/Le = of-gf3J
(13.1)
the present discussion, since deviations
g-values from ge can be accounted for
by
13.1 THE
CONDITION
introduction
coupling.
Here
J RESONANCE
(in unitsof
ofspin-orbit
h/27T,
where
h = Planck's constant) is the total angular momentum
Magnetic
moments constant
can be detected
by theirg-factor,
interactions
with magneticsplitting
fields.
vector,
is
a dimensionless
(the
g-value,
or spectroscopic
The gelectron
is a charged particle
with
angular
momentum (orbital
and spin) and,
In zero
field,
magnetic the
moments magneton.
of unpaired electrons
in a sample are randomly
factor),
and
isthe
a constant,
it f3possesses
a magnetic Bohr
moment, /Le' given The
by negative sign in Equation 13.1
as such,
In the presence of a magnetic field H, electron moments assume orientais aoriented.
consequence
of negative electronic charge. Neglecting orbital angular momentum
tions with respect to the applied field,
(Zeeman
/Le = giving
-gf3J rise to 2S + 1 energy states (13.1)
and considering only the total spin angular momentum S, Equation 13.1 can be
splitting). The measurable components of /Le are gf3m s where m s is the magnetic spin
Here as
J (in units of h/27T, where h = Planck's constant) is the total angular momentum
written
quantum
number, which can take the values +S, +(S - 1), ... , -(S - 1), -S.
vector, g is a dimensionless constant (the g-value, g-factor, or spectroscopic splitting
(13.2)
/Le an
= S-gf3S
The application
a magnetic
= 1/2
(ornegative
larger) system
is said to remove
factor),
and f3 is aofconstant,
thefield
Bohrtomagneton.
The
sign in Equation
13.1
spin degeneracy
(i.e.,
the
equal
energy
values
of m.
in the angular
absencemade
of aninapplied
Thethe
for
the
electron,
ge,
is
2.0023.
The
approximation
Equais g-value
a consequence
offree
negative
electronic
charge.
Neglecting
orbital
momentum
TABLE 13.1. Spectrometer Frequencies and g., Resonance Field Strength
field).for
and
considering
only
thediscussions
total spin angular
momentum
13.1free
canradicals
be
tionmagnetic
13.2
is valid
most
of the ESR
spectra S,ofEquation
the organic
The
an electron
moment
in aangular
magnetic
field is given
bybe considered
as energy of
andwritten
transition-metal
complexes
whose
orbital
momentum
can
Spectrometer Frequency
to be "quenched." Treating the g-value
an experimental quantity does not
harm
(13.3)
-/LeH
(13.2)
/LeE ==as
-gf3S
v(Hz)
Designation
A(cm) from ge can be accounted for by
the The
present discussion,
since
deviations
of
g-values
for the
free
electron,
ge, is13.3,
2.0023.
The approximation made in EquaUpong-value
combining
Equation
13.2 and
the expression
introduction
spin-orbit
tion 13.2 isof
valid
for mostcoupling.
discussions of
the ESR spectra of the organic free radicals
x 10E9 = gf3Hm.
X-band
3.156
0.317
3390
(13.4)
moments
can bewhose
detected
byangular
their interactions
with
magnetic
fields.
and Magnetic
transition-metal
complexes
orbital
momentum
can
be
considered
9
x 10
K-band
1.303
0.767
8207
In zero
the
magnetic
ofof
electrons
in
a sample
are
to be field,
"quenched."
Treating
the g-value
as
experimental
quantity
does
notrandomly
harm
9 unpaired
x 10
Q-band
results
(assuming
that
themoments
direction
theanapplied
field1.168
defines
the
z-axis).
When
0.856
12,489
the= present
discussion,
g-values
from ge can
be accounted
by
oriented.
the
presence
of deviations
a magnetic
H, electron
moments
assumefororientaS
1/2,Inthere
are
two since
energy
levels offield
introduction
spin-orbit
coupling.
tions
with respect
to
applied
field, giving
rise
to 2S + Oersteds
1 energy
a. of
For
thethe
purposes
of magnetic
resonance
spectroscopy,
(oe)states
and (Zeeman
(13.5)
Gauss
(G) are effectively
and
employed
interchangeably.
moments
can
bethe
by
interactions
with magnetic fields.
Edetected
+1/2
=
+tgf3H
msame
splitting). Magnetic
The
measurable
components
of
/Learetheir
are
gf3m
s where m s is the magnetic spin
In zero number,
field, the magnetic
moments
of unpaired
electrons
randomly
quantum
which can
take the
values +S,
+(Sin -a sample
1), ... ,are
-(S
- 1), -S.
and
oriented.
In the presence of a magnetic field H, electron moments assume orientaThe application
of13.1.
a magnetic
field
toand
anspectra
S = 1/2
(or larger)
system is Energy
said to remove
FIGURE
Energy
levels
in ESR
spectroscopy.
tions with
respect
to the
applied
field,
giving rise
to 2S
+ 1 energy A:
states (Zeeman
the splitting).
spin degeneracy
(i.e.,
the components
equal
energy
values
of m.
in B:
the
absence
of an(13.6)
applied
levels
an
unpaired
electron
inofa/Le
magnetic
ESR
absorption
Thefor
measurable
are gf3mfield.
where
m
is
the
magnetic
spin
s
s
magnetic
field).
RFispower
(P)
absorbed
vs.on
magnetic
field.
first-derivative
peak:
H. The
separation
whose
energy
linearly
dependent
quantum
number,
which
can
take the
values
+S,
+(SC:- ESR
1),between
...
, -(Sthese
- 1),energy
-S.
presentation-change
of
power
absorbed
perlarger)
unit
change
in
magnetic
The
energy
ofaat
an
moment
magnetic
field
byto remove
(Fig.
13.1)
a electron
particular
value
the
magnetic
field,
H Ris, isgiven
Thelevels
application
of
magnetic
field
to anof
S in
= a1/2
(or
system
is said
is thevalues
peak-to-peak
line
width.
The
firstvs. magnetic
field.
the spin field
degeneracy
(i.e., the
equal/1H
energy
of
m.
in
the
absence
of
an
applied
(13.3)
E = -/LeH
(13.7)

13.1

.=

Magnetic Field
A

HR
I
I
I

I
I
I

Magnetic Field
B

Magnetic Field

a. For the purposes of magnetic resonance spectroscopy, Oersteds (oe) and

Gauss (G) are effectively the same and are employed interchangeably.

and
(13.6)
whose energy is linearly dependent on H. The separation between these energy
levels (Fig. 13.1) at a particular value of the magnetic field, H R , is
(13.7)
In an ESR experiment, an oscillating magnetic field perpendicular to H R induces
transitions between the m. = -1/2 and m. = + 1/2 levels, provided the frequency,
v, is such that the resonance condition
TABLE

13.1.

dE = hv = gf3HR

Spectrometer Frequencies and g., Resonance Field Strength

(13.8)

is satisfied. The frequency is held constant and the magnetic field is varied. At a
particular value of the magnetic field, H R , resonance absorption of energy occurs,
Spectrometer
Frequency
resulting in a peak in the spectrum
(Fig. 13.1B).
The frequencies commonly employed
in ESR experiments are in the microwave region; these frequencies and magnetic field
strengths for g. resonance
v(Hz)absorption signals
Designation
A(cm) are given in Table 13.1.

x 109
X-band
3.156
0.317
3390
13.2 ESR INSTRUMENTATION
x 109
K-band
1.303
0.767
8207
9
Q-band
0.856the instrumentation
12,489 in ESR
1.168
As in most other types x of10spectroscopy,
employed

and

spectroscopy consists of a source of electromagnetic radiation, a sample holder, and

detection
equipmentresonance
for monitoring
the amount
of radiation
a. appropriate
For the purposes
of magnetic
spectroscopy,
Oersteds
(oe) andabsorbed
by the
In ESRthe
spectroscopy
a magnetic
field
provided by an electromagnet
Gauss
(G)sample.
are effectively
same and are
employed
interchangeably.
is also required. Monochromatic radiation of the various frequencies employed in
ESR work (Table 13.1) is obtained from klystrons, which are electronic oscillators

Electron Spin Resonance Spectrometer (ESR)

Electron Spin resonance spectroscopy is based on the

absorption of microwave radiation by an unpaired
electron when it is exposed to a strong magnetic field.

Species that contain unpaired electrons (namely free

radicals, odd-electron molecules, transition metal
complexes, rare earth ions, etc.) can therefore be
detected by ESR.

WORKING PRINCIPLE :
When an atomic or molecular system with unpaired electrons is subjected to a
magnetic field, the electronic energy levels of the atom or molecule will split into
different levels.
The magnitude of the splitting is dependent on the strength of the applied magnetic
field.
The atom or molecule can be excited from one split level to another in the presence of
an external radiation of frequency corresponding to the frequency obtained from the
difference in energy between the split levels. Such an excitation is called a magnetic
resonance absorption.
The atom or molecule under investigation may be in different environments in an actual
sample.
The magnetic resonance frequency will hence be influenced by the local environment
of the atom or molecule.
The electron spin resonance technique is therefore, a probe for a detailed identification
of the various atomic and molecular systems and their environments and all associated
parameters.

302

B.M. Weckhuysen et al.

Fig. 4ac. a General layout of an ESR spectrometer; b Block diagram of an ESR spectrometer
and c Magnetic and electric field patterns in a standard ESR cavity (reprinted from reference
[15]. Copyright 1992 Bruker Instruments, Inc.)

the cavity to increase sensitivity. Feeding the coils from an oscillator superimposes
a variable amplitude sinusoidal modulation on the slowly varying magnetic field.
The signal detected by the phase-sensitive detection system is proportional to the
slope of the ESR absorption as the magnetic field passes through resonance. The
recorder then presents the first-derivative spectrum. Many spectrometers are also
equipped to present second-derivative spectra.

Attenuator
Klystron

Sample

==TI==
Cavity

1--.."...-----"-.-1

Amplifier

Crystal
Detector

Waveguide
Modulation
Coils

FIGURE

13.2.

Electromagnet

Oscillator

Block diagram of a simple ESR spectrometer.

The sample tube must be chosen with careful attention to the physical, chemical,
and magnetic properties of each sample. For instance, when the sample is dissolved
in a polar solvent with an appreciable dielectric constant, quartz sample tubes are
usually not suitable and capillaries or thin rectangular cells of glass are used. Again,
when studying free radicals with g ge, Pyrex tubing can be used, whereas only

ESR spectroscopy consists of a source of electromagnetic radiation, a sample holder,

and appropriate detection equipment for monitoring the amount of radiation absorbed
by the sample.

In ESR spectroscopy a magnetic field provided by an electromagnet is also required.

Monochromatic radiation of the various frequencies employed in ESR work is

obtained from klystrons, which are electronic oscillators producing microwave
energy.

Spectrometers operating at X-band (3-cm wavelength) are the ones most commonly
employed.

The microwave radiation is transmitted along hollow rectangular metal pipes called
waveguides.

The sample is placed at the center of the sample cavity where the magnetic
vector is at a maximum.

Quartz tubes (~3 mm o.d.) are generally employed to contain solid and solution
samples.

Unlike the NMR technique, the sample tubes are not rotated.

The magnetic field is slowly and linearly increased until the resonance
condition is satisfied, at which point power is absorbed by the sample and a
change in current in the detector crystal is monitored.

A pair of Helmholtz coils are mounted around the cavity to increase sensitivity.

Feeding the coils from an oscillator superimposes a variable amplitude sinusoidal

modulation on the slowly varying magnetic field.

The signal detected by the phase-sensitive detection system is proportional

to the slope of the ESR absorption as the magnetic field passes through
resonance.

The recorder then presents the first-derivative spectrum. Many spectrometers

are also equipped to present second-derivative spectra.

The sample tube must be chosen with careful attention to the physical,
chemical, and magnetic properties of each sample.

For instance, when the sample is dissolved in a polar solvent with an

appreciable dielectric constant, quartz sample tubes are usually not
suitable and capillaries or thin rectangular cells of glass are used.

Again, when studying free radicals with g = ge, Pyrex tubing can be
used, whereas only quartz can be used for triplet (S =1) compounds
because of paramagnetic impurities such as Fe3 + in most laboratorygrade glassware.

Finger sized Dewar flasks (of the appropriate materials) and other
cryogenic equipment permit ESR spectra to be obtained as a function
of temperature.

In any ESR experiment it is important to monitor the microwave frequency at which

the spectrometer operates and the magnetic field range swept during the experiment.

Although the frequency is constant during an experiment, the frequency available

from a given klystron will vary a little with tuning of the instrument.

The frequency can be determined using a built-in frequency meter or appropriate

transfer oscillators and frequency counters.

The magnetic field can be monitored using an NMR gaussmeter or by using samples
of known g-value; for instance, the DPPH free radical for which g = 2.0036.

The magnetic field sweep can also be checked using Fremy's radical or oxobis(2,4pentanedionato)vanadium(IV).

APPLICATIONS :
Electron

Spin Resonance, ESR, is a powerful non-destructive and non-intrusive analytical

method.
ESR yields meaningful structural information even from ongoing chemical or physical processes,
without influencing the process itself.
It is the ideal technique to complement other analytical methods in a wide range of application
areas.
One can perform studies related to :

Molecular structure

Crystal structure

Reaction kinetics

Valence electron wave functions

Molecular motion

Relaxation properties

Electron transport

Crystal / ligand fields

Reaction mechanisms etc.