Electron Spin Resonance

Introduction
Electron spin resonance was discovered by Zavoisky in 1945. 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. By this technique we can study properties of
solids including
(a) Energy levels of paramagnetic ions in crystals.
(b) Energy levels of unpaired electrons in semi-conductors and organic free radicals.
(c) Color centres and radiation damage centres.
(d) Ferro and antiferro-magnetic materials.

Theory
The theory underlying electron spin resonance is virtually identical to that for nuclear magnetic resonance of
protons, so only a brief summary will be given here. Details can be obtained from the theory for the NMR
experiment.
−
→ −→
When a magnetic field B0 is applied to an electron the moment − →μ will precess around B0 with the angular
Larmor frequency ω0 given by

ω0 = γB0 (1)
e
Where γ is the gyromagnetic ratio and given by g( 2m );
for free electron it is 176 GHz/Tesla. Now if
e
we apply an oscillatory weak magnetic field B1 at the Larmor frequency ω0 in the x-y plane, i.e. in a plane
−
→
perpendicular to B0 , transitions can take place between the Zeeman levels. This is best illustrated in the
→
− →
−
quantum picture of the Zeeman effect. For an electron with spin S and orbital angular momentum L , in the
→
−
L-S coupling scheme, we get a resultant moment J . When a magnetic field is applied, the 2J+1 sublevels
split up to give equal energy differences ΔE between adjacent levels given by

ΔE = ω0 = gJ μB B0 (2)
e
where μB = 2me = Bohr Magneton(in SI unit) and gJ = Landé g factor which is given by

J(J + 1) + S(S + 1) − L(L + 1)

gJ = 1 + (3)
2J(J + 1)

If the alternating magnetic field is at the proper frequency ν0 such that ΔE = hν0 , then the transitions
will take place between adjacent sublevels according to the selection rule Δm = 0, ±1 for magnetic dipole
transitions. Thus the condition for resonance is

ΔE = hν0 = gJ μB B0 (4)

For the determination of Spectroscopic spliiting factor g (for free electron), we can use equation4.

1
 Experimental Techniques and Apparatus

Oscilloscope

Sample

Magnetic coils

ESR Module
Control Panel

Sensitivity

Figure 1: ESR Setup in Lab

On the control panel, set the smallest frequency at which a defined resonance absorption signal can be
observed (approx. 38 MHz). Adjust the "SENSITIVITY" control so as to maximize the signal level
(At the optimal setting, the LED flickers faintly. If the LED shines brightly, the signal is overdriven).
Read the resonance coil voltage UR with the help of the cursor on the oscilloscope. Repeat the
measurement for various frequencies between 38 and 74 MHz in 5 MHz increments, and enter the
respective, set frequencies as well as the measured resonance coil voltages in a Table.

Figure 2: Schematic sketch for reading the resonance coil voltage UR from the oscillogram.
Absorption signal (red) and the magnetic field trace over time (yellow) for electron spin resonance in
DPPH.
In this experiment, electron spin resonance will be demonstrated in diphenyl-picrylhydrazyl (DPPH),
an organic compound, the molecules of which include an unpaired electron. The basic magnetic field
is generated inside a pair of Helmholtz coils and is moved between zero and a maximum value of Bmax
~ 3.67 mT (Check ESR Module) using a saw-tooth wave-form. Now it is possible to look for a
frequency 𝜈0 , at which resonance absorption takes place at a distinct position along the saw-tooth
curve, i.e. for a pre-selected magnetic field. Increasing the frequency shifts the resonance absorption
toward larger magnetic fields

From the resonance coil voltages UR (Table), calculate the magnetic fields as follows:

B0 = Bmax mT/V. UR (5)

1. Obtain the resonance peaks.

2. Set frequencies between 38 and 74 MHz.
3. Adjust the sensitivity control so as to maximize the signal level.
4. Calculate the corresponding magnetic field using equation (5).
5. Plot a graph of magnetic field against frequency.
6. Determine the Landé g factor.
7. Repeat the experiment for different frequencies. Compare the obtained g values.
8. Do error analysis by least square method or graphical method.

Safety and Precautions:

1. Mobile phones interfere with the measurement; therefore no mobile phones should be near the
device during the experiment.
2. Do not shake the sample or Helmholtz coils. Always handle the DPPH sample (orange cap)
with care! DPPH can cause allergic skin reactions.
3. Always be careful when connecting and disconnecting the measuring probe cable.
4. Change the frequency/sensitivity knob slowly.
5. Set the sensitivity to where the maximum signal amplitude is obtained. (At the ideal setting,
slight flickering of the LED may be observed. If the LED lights up brightly, the signal is
overloaded.

References:

1. Zavoisky E., J. Phys.USSR 2, p 211 (1945)

2. Ingram D.J.E., Spectroscopy at Radio and Microwave Frequencies, Butterworths, II Ed. (1962)
3. Pake G.E., Paramagnetic Resonance, Benjamin (1962)
4. Orton J.W., Electron paramagnetic resonance, London Iliffee Books Ltd. (1968)
5. Al tshuler S.A. and Kozyrev B.m., Electron paramagnetic resonance, (English Translation),
Acad.Press (1964)
6. Assenhein H.M., Introduction to E.S.R., Holger & Watt, London (1966)
7. Alger R.S., Electron Paramagnetic Resonance Techniques and Applications, Interscience
Publishers (1968)
8. Andrew E.R., Nuclear Magnetic Resonance, Cambridge University Press (1955)
9. Melissions A.C., Experiments in Modern Physics, Acad. Press, New York & London(1967)