Electron Spin Resonance

Diptanil Roy1
1

National Institute of Science Education and Research, Bhubaneswar

(Dated: November 4,2016)

This experiment deals with the investigation of the magnetic momentum of the electron spin.
Consequently the measurement of the Lande g-factor in the case of the given compound DPPH
(Diphenylpicrylhydrazyl ) was performed.Further the, measurement of the FWHM(Full width half
maximum) line of the absorption line of the spectrum was obtained by measurement of the magnetic
displacement B. The results were then compared with the standard values.

I.INTRODUCTION

Electron spin resonance (ESR) has developed over the

past several decades as a technique to provide information on the electronic structure of organic, inorganic, biological, solid state, and surface molecular species. These
include organic free radicals,b-iradicals, triplet excited
states, and most transition metal and rare earth species.
These can be studied accurately because the ESR signal
is perturbed by the fields produced by the surrounding
lattice. Biological applications, in addition to studies of
these organic and inorganic species in biological systems,
include the use of spin labels as probes of molecular environment in enzyme active sites and membranes. Point
defects in solids and, increasingly, active chemical species
on surfaces of catalysts are also investigated using ESR.
ESR is an important spectroscopic technique for the
study of paramagnetic species (unpaired electrons)
such as free radicals, metal complexes, or triplet excited
states of diamagnetic molecules.

the nitrogen atom is in the DPPH molecule,the orbital

motion is almost zero and is said to be quenched. This
is brought about by fields produced by the surrounding
lattice, which lift the degeneracy of the angular momentum states and block the precession of the magnetic moment. The electron behaves almost like an electron with
no orbital angular momentum. Paramagnetic subtances
have atoms with unpaired electrons and these atoms have
magnetic moments If these magnetic moments do not interact strongly enough to produce ferromagnetism (i.e.,
magnetic domains), the magnetic moments are randomly
oriented if no external magnetic field B is present. The
magnetic moment of an electron is the result of adding
its orbital and spin magnetic moments in an appropriate
way.
The magnetic moment of the electron due to its spin(
we assume in z direction) is:
sz = B gSz .
where B is the Bohr Magneton, magneton, e is the electronic charge, me is the mass of the electron, g is the spin
Lande factor and Sz = 21 ~ is the z component of the
electron spin.

FIG. 1: Diphenylpicrylhydrazyl

In this case the compound DPPH (Diphenylpicrylhydrazyl) has been used. DPPH (Diphenylpicrylhydrazyl)
is an organic, paramagnetic material with one stable radical. The magnetic moment of the molecule is determined
only by the spin moment of the valence in the N-bridge
as shown in 1. In a free nitrogen atom, 6 electrons pair
off and contribute no orbital or spin angular momentum.
Nor do these electrons as a whole have a net magnetic moment. The 7th electron is in a 2p state and has one unit
of orbital angular momentum with an orbital quantum
number of l = 1. There is a magnetic moment associated
with this electron due to both its orbit and spin. When

FIG. 2: Energy Level splitting due to applied B field.

If we apply a magnetic field in the z-direction the spin

magnetic moment give rise to two different energy states
given by potential energy U = sz .B:
U =

1 e
B gB
2 2me

2
Thus, for an electron,the alignment can either be along
the direction (parallel) to the magnetic filed which corresponds to the lower energy state ms = 21 or opposite
(anti-parallel) to the direction of the applied magnetic
field ms = + 12 . The two alignments have different energies and this difference in energy lifts the degeneracy of
the electron spin states.Figure 2.
In electron spin resonance (ESR), an oscillating magnetic field is used to induce transitions between energy
levels.If an oscillating magnetic field is applied with a frequency that corresponds to the energy difference between
the levels as allowed by the selection rules, photons will
be absorbed as transitions are made from the lower energy level to the upper one, and photons will be emitted
as transitions are induced from the upper level to the
lower one. In thermal equilibrium, there will be slightly
more electrons in the lower state than the upper one, as
given by the Boltzmann factor. Thus, there will be a net
absorption of energy from the oscillating magnetic field
which is seen as a trough in the oscilloscope.
The selection rule for magnetic transitions of the electron spin resonance experiment is:

1. ESR resonator with field coils

2. ESR power supply
3. Universal Power supply
4. Oscilloscope, 30 MHz, 2 channels
5. Digital multimeter
6. Screened cable, BNC, (4 No.)
7. Adapter, BNC-socket/4 mm plug pair
8. Connecting cords

mj = 1
Where mj is the magnetic quantum number.
This leads to the absorption condition:
E = B gj B = hf
Where h is the Plancks constant, B is the magnetic field,
f is the frequency and gj is the Lande g factor.
In many cases, especially with molecular radicals, the
angular momentum L of the unpaired electron is extinguished by the electric fields of the neighbouring atoms
and molecules. In the case of DPPH, L = 0 and therefore
theoretically gj is =2
The given magnetic field is applied via a Helmholtz
coil of 241 turns and radius R = 0.048 m.On applying
a current I, it produces a magnetic field along its axis
Given by the formula:
B = 4.0642 103 I

T
.
A

Correspondingly, the FWHM is given by:

B = 4.0642 103 I

T
.
A

FIG. 3: Wiring Diagram of the setup

The formula for Lande G factor is:

g=

2.565
Ir

Where Ir is the resonance current.

II.WORKING AND APPARATUS

The setup consists of the following components.:

The connections between the various components are as

shown in 2.
The Setup of the apparatus is as shown in 3 The first
stage of the ESR circuit consists of a critically adjusted
radio frequency oscillator. This type of oscillator is required here, so that the slightest increase in its load decreases the amplitude of oscillation to an appreciable extent. Its output is fed into a cavity which allows standing

Ir =1.24 A
. Using our working formula, the value of g was found
to be:
g=2.0685
FIG. 4: ESR Setup

. The sensitivity of the X and Y channels were fixed at

X=0.5 V/cm, Y=0.1 V/cm.

waves at certain frequencies. When the frequency of oscillation becomes equal to the frequency corresponding
to the energy splitting of the sub-levels(Resonance), the
oscillator amplitude registers a dip due to the absorption
of power by the sample. When the frequency of oscillator
reaches 146 MHz, resonance is achieved. This is possible due to the use of quartz crystals which can generate
very sharp frequencies.There is also a phase shifter which
can be used to reduce any change in the phase difference
which may be introduced in the amplification stages of
the spectrometer and oscilloscope.
The output is monitored from the oscilloscope which
is set in X-Y configuration. At resonance, there is a dip
in the graph displayed by the oscilloscope.

. This was not changed throughout the experiment.

Height of the peak was found to be 2 units. After centering the peak on the y axis and positioning the flat
region at 1 unit above the X axis, the intersection points
on the X- axis were found to be.
Left=-0.1 unit Right=0.1 unit.
With corresponding current:
Ilef t = 0.07 A Iright = 0.14 A
.
The FWHM was found to be
FWHM = 2.845 10-4 T/A
.

III.DATA,TABULATION AND CALCULATION

Fig. 5 shows the dip in the graph of the oscillator at

resonant current. The image is processed to provide a
clear and sharp image. The actual photographs taken in
lab are in the Appendix.

IV.ERROR ANALYSIS

The least count of the multimeter was 0.01 A. So the

error in g is:
I
2I
8.3 103

g = g

0.008
So g is: 0.008.
The error in magnetic displacement is:
I
2I
1.1 106

B = B

0.01 104 T /A
So (B) is: 0.01 10-4 T /A.

V.CONCLUSION

FIG. 5: Lissajous Figure at resonance condition in the Oscilloscope

The corresponding resonance current was found to be:

The literature value of the Land

e g factor is 2.0037
for a single electron. Compared to this, the experimental
g factor was found to be 2.06850.008.
The literature value of FWHM or the magnetic
displacement is 2.8 10-4 T/A.

4
In our experiment, the FWHM was found to be 2.845
10 0.01-4 T/A.

APPENDIX

The obtained values are quite close to the literature values and are in good agreement with them.
The Lissajous Figure obtained on the oscilloscope is not
exactly sharp due to fluctuations in the input power to
the ESR setup caused by A/C and Fan in the lab. It
can be reduced by using a more stable integrated power
supply. More accurate results can be obtained by using
larger coils which can reduce fringing effects and act as
more ideal Helmholtz coils.

[1]
[2]
[3]
[4]

PHYWE instrumentation manual.

http://www.its.caltech.edu/ derose/labs/exp6.html
www.cmi.ac.in/ ravitej/lab/esr
www.physics.usyd.edu.au/ senior-lab/3YL/Expt15

FIG. 6: Lissajous Figure(original)