Atomic & Molecular Physics

Unit-5
Electron Spin Resonance (ESR)
Spectroscopy
Dr. ANUJ KUMAR
Deptt of Physics, Chaudhary Charan
Singh University, Meerut
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Course Name: Atomic & Molecular Physics

M.Sc. Physics (II Sem)
Instructor: Dr. Anuj Kumar
 Electron Spin Resonance Spectroscopy

 It is a branch of absorption spectroscopy in which

radiation having frequency in microwave region is
absorbed by paramagnetic substance to induce
transition between magnetic energy level of electron
with unpaired spins.
 Magnetic energy splitting is done by applying a static
magnetic field.
 Absorption spectroscopy, operate at microwave
frequency 104– 106MHz (~1.0 J mol-1)
• ESR Phenomenon is shown by:

1. Atoms having odd number of electrons.

2. Ions having partly filled inner electron shells
3. Other molecules that carry angular momentum of
electronic origin.
4. Free radicals having unpaired electrons.
5. Molecules with paired electrons and zero magnetic
field.
 ESR is also known as Electron Paramagnetic
Resonance(EPR) or Electron Magnetic
Resonance(EMR).
 Paramagnetic substances are those which contains
unpaired electrons having equal and opposite spins.
 They are of two types:
1. Stable paramagnetic substances. Eg. NO, O2, NO2.
2. Unstable paramagnetic Substances Eg. Free
radicals.
Theory of ESR
 In ESR the energy levels are produced by the
interaction of magnetic moment of an unpaired electron
in a molecule or ion with an applied magnetic field.
 Required frequency of radiation dependent upon strength of
magnetic field
 Common field strength 0.34 and 1.24 T
 9.5 and 35 GHz
 Microwave region
 The ESR spectrum results due to the transitions
between these energy levels by absorbing radiations of
microwave frequency.
 The unpaired electrons are excited to a high energy state
under the magnetic field by the absorption of microwave
radiations.
 The excited electron changes its direction of spin and
relaxes in to the ground state by emitting its energy.
 The transition between two different energy levels takes
place by absorbing a quantum of radiation of frequency
in the microwave region.Unlike most traditional
spectroscopy techniques, in EPR spectroscopy the
frequency of the radiation is held constant while the
magnetic field is varied in order to obtain an absorption
spectrum.
 Microwave absorption is measured as a function of the
magnetic field by ESR Spectroscopy.
Energy Levels
•The unpaired electrons
are excited to a high
energy state under the
magnetic field by the
absorption of microwave
radiations.

•The excited electron

changes its direction of
spin and relaxes in to the
ground state by emitting
its energy.

•The transition between

two different energy
levels takes place by
absorbing a quantum of
radiation of frequency in
the microwave region.
 When absorption takes place:
2µe H =hv
 Where v =frequency of absorbed radiation in cycles/second.
 The energy of transition is given by
∆E = hv =g µBH
Where h = Plank’s constant
H = Applied magnetic filed
µB = Bohr’ s magneton which is a factor for converting
angular momentum into magnetic moment.

The value of µB is given as µB= eh/4πmc

Where, e = electric charge
m = mass of electron
c = velocity of light
 Proportionality Factor
 Measured from the center
of the signal
 For a free electron
 2.00232
 For organic radicals
 Typically close to free-
electron value
 1.99-2.01
 For transition metal compounds
 Large variations due to spin-orbit coupling and zero-field
splitting
 1.4-3.0
10
Instrumentation

 Source
 Circulator or Magic -T
 Sample Cavity
 Magnet System
 Crystal Detector
 Auto amplifier and Phase sensitive Detector
 Oscilloscope and Pen Recorder
Source:
 Klystron

It is a vacuum tube which can produce microwave

oscillations centered on a small range of frequency

The frequency of the monochromatic radiation is

determined by the voltage applied to Klystron.
Isolator:

 It is a non reciprocal device which minimizes vibrations

in the frequency of microwaves produced by Klystron
oscillator.
 The variations occur in the frequency due to the
backward reflections in the region between the Klystron
and circulator.
 Isolator is a strip of ferrite material.
Wave meter
 It is fixed in between the isolator and attenuator to
know the frequency of microwaves produced by
Klystron oscillator.

 Usually it is calibrated in frequency units instead of

wavelength.
Attenuator:

 Attenuator is used to adjust the level of the

microwave power incident upon the sample.

 It processes an absorption element and corresponds

to a neutral filter in light absorption measurement.
 Magic T or Circulator:

•Microwave radiations
finally enter to the
circulator through a
wave guide by a loop
wire which couples
with oscillating
magnetic field and
setting a corresponding
field.
Sample Cavity:
 This resonant cavity which contains the sample is
called the heart of ESR.
 It is constructed in such a way to maximize the
applied magnetic filed along the sample dimension.
 In most ESR spectrometer dual sample cavities are
used for simultaneous observation of sample and
reference materials.
Magnet System:

 The sample cavity is placed between the pole pieces

of an electromagnet
 This provides a homogenous magnetic field and can
be varied from zero to 500 gauss.
 The stability of the field is achieved by energizing the
magnet with a highly regulated power supply.
Crystal Detectors:
 The most commonly used detector is a silicon crystal
which acts as a microwave rectifier.
 This converts microwave power into a direct current
input.

Oscilloscope and Pen Recorder

 The signal from phase sensitive detector and sweep unit
is recorded by the oscilloscope or pen recorder.
ESR Spectrometer:
 Working:
 The Klystron oscillator is set to produce microwaves.
 After passing though the isolator, wave meter and attenuator the
microwaves are entered into the circulator on magic T
 Then it reaches the detector which acts as a rectifier, ie.
converting the microwave power into the direct current.
 If the magnetic field around the resonating cavity having the
sample is changed to the value required for the resonance, the
recorder will show an absorption peak.
 If the magnetic field is swept slowly over a period of several
minutes, the recorder will show the derivative of the microwave
absorption spectrum against magnetic field as shown below:
 peak
Intensity

Magnetic field
Derivative signal

Magnetic field
Presentation of ESR Spectrum:
 The ESR spectrum is obtained by plotting intensity against
the strength of a magnetic field.
 The better way is to represent ESR spectrum as a derivative
curve in which the first derivative(slope) of the absorption
curve is plotted against the strength of the magnetic field
 The total area covered by either the absorption or
derivative curve is proportional to the number of unpaired
electrons in the sample.
 In order to find out the number of electrons in an
unknown sample, comparison is made with a standard
sample having a known number of unpaired electrons and
possessing the same line shape as the unknown.
 The most widely used standard is 1,1-diphenyl-2-
picrylhydrazyl free radical(DPPH)
Determination of g value:
 The best method of measurement of g value is to
measure the field separation between the center of the
unknown spectrum and that of reference substance
whose g value is already known.
 DPPH is generally used a standard whose g value is
2.0036.
 In the spectrometer standard sample is placed along with
the unknown sample in the same chamber of dual cavity
cell.
 The spectrum will show signals with a filed separation of
∆H.
 The g value of unknown sample is given
g = gs [ ∆H/H ]
 Hyperfine Interactions
 EPR signal is ‘split’ by neighboring nuclei
 Called hyperfine interactions
 Can be used to provide information
 Number and identity of nuclei
 Distance from unpaired electron
 Interactions with neighboring nuclei
E = gmBB0MS + aMsmI
a = hyperfine coupling constant
mI = nuclear spin quantum number
 A is measured as the distance between the
centers of two signals
 Which nuclei will interact?
 Selection rules same as for NMR
 Every isotope of every element has a ground state nuclear spin
quantum number, I
 has value of n/2, n is an integer
 Isotopes with even atomic number and even mass number have I
= 0, and have no EPR spectra
 12C, 28Si, 56Fe, …

 Isotopes with odd atomic number and even mass number have n
even
 2H, 10B, 14N, …
 Isotopes with odd mass number have n odd
 1H, 13C, 19F, 55Mn, …
 Hyperfine Interactions

Interaction with a single nucleus of spin ½

Ebsworth, E. A. V.; Rankin, David W. H.; Cradock, Stephen Structural Methods in
Inorganic Chemistry; CRC Press: Boca Raton, 1987.
Hyperfine Interactions
 Coupling patterns same as in NMR
 More common to see coupling to nuclei with spins greater
than ½
 The number of lines:
2NI + 1
N = number of equivalent nuclei
I = spin
 Only determines the number of lines--not the intensities
Hyperfine Interactions
 Relative intensities determined by the number of interacting
nuclei

 If only one nucleus interacting

 All lines have equal intensity

 If multiple nuclei interacting

 Distributions derived based upon spin
 For spin ½ (most common), intensities follow binomial
distribution
 Relative Intensities for I = ½
N Relative Intensities
0 1
1 1:1
2 1:2:1
3 1:3:3:1
4 1:4:6:4:1
5 1 : 5 : 10 : 10 : 5 : 1
6 1 : 6 : 15 : 20 : 15 : 6 : 1
Relative Intensities for I = ½
 Relative Intensities for I = 1
N Relative Intensities
0 1
1 1:1:1
2 1:2:3:2:1
3 1:3:6:7:6:3:1
4 1 : 4 : 10 : 16 : 19 : 16 : 10 : 4 : 1
5 1 : 5 : 15 : 20 : 45 : 51 : 45 : 20 : 15 : 5 : 1
6 1 : 6 : 21 : 40 : 80 : 116 : 141 : 116 : 80 : 40 : 21 : 6 : 1
Relative Intensities for I = 1
Hyperfine Interactions
 Example:
 VO(acac)2
 Interaction with vanadium nucleus

 For vanadium, I = 7/2

 So,
2NI + 1 = 2(1)(7/2) + 1 = 8

 You would expect to see 8 lines of equal intensity

Hyperfine Interactions

EPR spectrum of vanadyl acetylacetonate

Hyperfine Interactions
 Example:
 Radical anion of benzene [C6H6]-

 Electron is delocalized over all six carbon atoms

 Exhibits coupling to six equivalent hydrogen atoms
 So,
2NI + 1 = 2(6)(1/2) + 1 = 7

 So spectrum should be seven lines with relative intensities

1:6:15:20:15:6:1
Hyperfine Interactions

EPR spectrum of benzene radical anion

Hyperfine Interactions
 Coupling to several sets of nuclei
 First couple to the nearest set of nuclei
 Largest a value

 Split each of those lines by the coupling to the next closest

nuclei
 Next largest a value

 Continue 2-3 bonds away from location of unpaired electron

Hyperfine Interactions
 Example:
 Pyrazine anion
 Electron delocalized over ring
 Exhibits coupling to two equivalent N (I = 1)
2NI + 1 = 2(2)(1) + 1 = 5
 Then couples to four equivalent H (I = ½)
2NI + 1 = 2(4)(1/2) + 1 = 5
 So spectrum should be a quintet with intensities 1:2:3:2:1 and
each of those lines should be split into quintets with intensities
1:4:6:4:1
Hyperfine Interactions

EPR spectrum of pyrazine radical anion

 Let us predict the E.S.R spectrum of the radical fragment CH CH2 • − It should
contain six lines - a large doublet arising from the interaction with the CH fragment
(producing two lines) and a smaller triplet due to the electron interacting more
weakly with the two remote protons of the CH2 fragment (producing three lines).
The resulting diagram is shown in Figure. In the case where the radical is CH CH2 •
− , the resulting pattern is also predicted to contain six lines, now triplet will have
large compare to doublets as shown in Figure
Conclusions
 Analysis of paramagnetic compounds
 Compliment to NMR
 Examination of proportionality factors
 Indicate location of unpaired electron
 On transition metal or adjacent ligand

 Examination of hyperfine interactions

 Provides information on number and type of nuclei coupled to
the electrons
 Indicates the extent to which the unpaired electrons are
delocalized
 Comparison of ESR with NMR
NMR ESR
 Different energy states are  Different energy states are
produced due to the alignment of produced due to the alignment of
the nuclear magnetic moments
the electronic magnetic
relative to applied magnetic field
and the transition between these moments relative to applied
energy states occurs on the magnetic filed and the transition
application of an appropriate between these energy states
frequency in the radio frequency occurs on the application of an
region.
appropriate frequency in the
 NMR absorption positions are
microwave region.
expressed in terms of chemical
shifts.  ESR absorption positions are
expressed in terms of “g” values.
 Nuclear spin spin coupling causes
the splitting of NMR signals.  Coupling of the electronic spin
with nuclear spins(hyperfine
coupling) causes the splitting of
ESR signals.
Applications of ESR spectroscopy:
Electron Paramagnetic Resonance ( EPR ), sometimes
referred to as Electron Spin Resonance ( ESR ), is a
widely accepted spectroscopic technique in various
research fields. This technique is used to study
paramagnetic centers on various oxide surfaces, which
are frequently encountered in heterogeneous catalysis.
The observed paramagnetic centers include surface
defects, inorganic or organic radicals, metal cations or
supported metal complexes and clusters. Each of these
paramagnetic species will produce a characteristic EPR
signature. Diamagnetic oxide materials can also be
studied using suitable paramagnetic probes, including
nitroxides and transition metal ions.
 Applications
Applications of ESR spectra:
 It decides the site of unpaired electrons.
 The number of line components decide about the
number and type of nuclei present in the neighborhood
of the odd electron.
 If the electric field is not spherical then the ESR spectrum
is anisotropic,ie the rotation of the sample shifts the ESR
spectrum.
 From this the g value can be measured by comparing the
position of the line with that of standard substance.
 Determination of type of nuclei which are responsible for
splitting pattern by comparing the relative intencities.
Applications of ESR spectroscopy:
 Study of Free radicals
 Even in very low concentrations also we can study the free
radicals by using ESR spectroscopy.
 Structure of organic and inorganic free radicals can be identified.
 Investigation of molecules in the triplet state.
 Spin label gives the information about polarity of its
environment.
 Structural Determination
 In certain cases ESR provides the information about the shape of
the radcals.
 Reaction Velocities and Mechanisms
 Study of inorganic compounds
 Study of catalysts
 Determination of oxidation state of a metal.
 Analytical applications:
 Determination of Mn2+
 Determination of vanadium.
 Determination of poly nuclear hydrocarbon.
 Biological applications:
 The presence of free radicals in healthy and diseased conditions.
 Functioning of most of the oxidative enzymes can be conformed.