ELECTRON SPIN RESONANCE (ESR)

INTRODUCTION

ESR IN THEORY

(a) ELECTRON SPIN RESONANCE (ESR)
Electron paramagnetic resonance (EPR) or Electron spin resonance (ESR) is a spectroscopic
technique which detects species that have unpaired electrons, generally meaning that the
molecule in question is a free radical, if it is an organic molecule, or that it has transition metal
ions if it is an inorganic complex.
When the molecules of a solid exhibit paramagnetism as a result of unpaired electron spins,
transitions can be induced between spin states by applying a magnetic field and then
supplying electromagnetic energy, usually in the microwave range of frequencies. The
resulting absorption spectra are described as EPR or ESR.
(b) RESONANCE CONDITION
For an electron, the magnetic moment associated with the total angular momentumJ

is:

J B
J
g
= J
| |
|
\ .

(1)
where

J
g : Lande splitting factor

B
: Bohr magneton
In a magnetic field
0
B

, the magnetic dipole moment interacts with it and the corresponding

potential energy is given by :

( )
J 0
J B 0 J
E= B
= g B m

(2)
with
J
m = +J, J-1, .., -J
Consider an electron for which the total angular momentum is just its spin. Then the angular
momentum quantum number is:
J = S =
1
2

and
J
g =
S
g

= 2.0023
Now equation (2) takes the form:

S B 0 S
E= g B m (3)
with
S
m =
1 1
,
2 2
+
The electron with only spin angular momentum can thus orient i tself in only two ways and an
appropriate frequency radiation can cause a transition from one spin state to the other. The
condition for resonance, therefore, is that the energy of the photons of the external radiation
matches the energy difference between the spin states of the electron.

S B 0
h = E = g B v A
or simply

S B 0
h = g B v (4) Resonance condition
wherev is the frequency of the incident radiation

ESR IN PRACTICE

In order to observe resonance, radio frequency radiation of appropriate frequency is required
to cause a transi tion from one spin state to the other. Practically, it is easier to set the
frequency of the electromagnetic radiation at some fi xed value and vary the magnitude of the
magnetic field about some constant value so that the resonance condition is satisfied.





















EXPERIMENTS

EXPERIMENT 1
Determining the resonance magnetic field
0
B as function of the selected resonance frequency
v and the g-factor of DPPH

Apparatus: ESR control uni t and probe uni t, Helmholtz coils, oscilloscope, ammeter , RF
probes, DPPH sample

Procedure: The ESR control uni t, probe uni t and Helmholtz coils are set up as shown in the
figure below:



For the 15-30 MHz RF probe, the resonance frequency is set at v =15 MHz. The modulation
amplitude U
mod
is set to the second scale marking and phase shift is set to 0. The voltage U
0

is slowly enhanced unti l the resonance signals are equally spaced and symmetric. The
oscilloscope is switched to the XY operation and phase shift is set so that the two resonance
signals coincide. This adjusts the resonance condition. The direct current 2I
0
through the pair
of Helmholtz coils is measured. The process is repeated by increasing the resonance
frequency continually in steps of 5 MHz (the plug-in coils 30-75 MHz and 75-130 MHz are
used). Magnetic field B
0
is calculated using I
0
and graph is plotted betweenv and B
0
. g-factor
is also obtained using the graph.

Observations and Calculations
For the Helmholtz coils:
Number of turns per coil = n =320
Radius of the coils = r = 6.8 cm
Magnetic field for current I = B
0
=
0
(4/5)
3/2
I n/r = (4.23mT) I/A
Frequency
(MHz)
2I
0

(A) Plug-in coil
B
0

(mT)
15.0 0.26 small 0.55
19.9 0.34 small 0.72
26.8 0.45 small 0.95
30.0 0.51 small 1.08
32.2 0.61 small 1.29
35.0 0.65 medium 1.37
40.0 0.74 medium 1.56
45.0 0.79 medium 1.67
50.1 0.86 medium 1.82
55.0 0.96 medium 2.03
60.0 1.06 medium 2.24
65.0 1.15 medium 2.43
70.0 1.21 medium 2.56
74.7 1.30 medium 2.75
75.0 1.33 big 2.81
80.0 1.42 big 3.00
85.0 1.46 big 3.09
90.0 1.56 big 3.30
95.2 1.64 big 3.47
100.2 1.77 big 3.74
105.3 1.85 big 3.91
110.3 1.96 big 4.14
115.0 2.02 big 4.27
120.0 2.10 big 4.44
125.0 2.19 big 4.63
129.6 2.29 big 4.84


RESONANCE FREQUENCY AS FUNCTION OF
MAGNETIC FIELD FOR DPPH
v = 26.975B
0
- 0.1329
0.0
20.0
40.0
60.0
80.0
100.0
120.0
140.0
0.00 1.00 2.00 3.00 4.00 5.00 6.00
Magnetic field B
0
(mT)
R
e
s
o
n
a
n
c
e

f
r
e
q
u
e
n
c
y




v
(
M
H
z
)



From graph:
v/B
0
= 26.97 MHz/mT
g-factor is thus obtained: g = h v /
B
B
0
= 1.93
Value quoted in literature: g = 2.0036
Percentage error = 3.67%












EXPERIMENT 2
Determining the line width o B
0
of the resonance signal

Apparatus: ESR control uni t and probe uni t, Helmholtz coils, oscilloscope, ammeter, RF
probes, DPPH sample

Procedure: The experimental set up is the same as for the experiment 1. XY operation of the
oscilloscope is selected and the resonance condition for v = 50 MHz is adjusted. The
resonance signal is extended in the X direction exactly over the total width of the screen by
varying the modulation voltage U
mod
. The RMS value of the current 2I
mod
is measured by
swi tching the ampere meter to AC. The width U of the resonance signal is measured at half
maxi mum.
Observations and Calculations
Hlaf-width read from the oscilloscope:
oU = (0.4 div)(2 V/div) = 0.8V
Calibration of the voltage U
mod
:
U
mod
= (6.8 div)(2 V/div) = 13.6V corresponds to 2 I
mod
= 0.7A (rms of AC)
Determining the half-width oB
0
:
oI = (oU / U
mod
).I
mod
= 0.058A
From this
oB
0
= (4.23mT)(oI / A) = 0.24mT
Value quoted in the literature: oB
0
= 0.15-0.18 mT



(ESR Experiments Lab Report by: Arooj Mukarram)