Electron Spin Resonance

SAMYAJIT GAYEN
14MS041
GROUP- A/10

IISER KOLKATA

AUG,2017
 Contents

1 INTRODUCTION 5
1.1 ABSTRACT . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.2 AIM OF THE EXPERIMENT . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.3 APPARATUS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5

2 THEORY AND WORKING FORMULA 6

2.1 BACKGROUND . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
2.2 ELECTRON SPIN RESONANCE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2.3 RELAXATION AND SATURATION . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
2.4 LINE WIDTH AND THE SPIN-SPIN AND SPIN-LATTICE INTERACTIONS . . . . . . . 9
2.5 WORKING FORMULA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9

3 EXPERIMENTAL SET UP AND BASIC CIRCUIT 10

3.1 BASIC CIRCUIT . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
3.2 RF oscillator . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
3.3 Test Sample . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11

4 OBSERVATION AND DATA ANALYSIS 12

4.1 OBSERVATION 1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
4.1.1 TABLE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
4.1.2 GRAPH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
4.1.3 CALCULATION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
4.2 OBSERVATION 2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
4.2.1 TABLE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
4.2.2 GRAPH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
4.2.3 CALCULATION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
4.3 OBSERVATION 3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
4.3.1 TABLE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
4.3.2 GRAPH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
4.3.3 CALCULATION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
4.4 RESULT . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16

2
5 ERROR ANALYSIS 17
5.1 ESTIMATION OF ERROR . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
5.2 SOURCE OF ERROR . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17

6 DISCUSSION AND CONCLUSION 18

3
 1

INTRODUCTION

1.1 ABSTRACT
ESR is basically transition of electron between the sublevels of the same energy level caused by the
presence of an external magnetic field.
Zavoisky in 1945 performed the earliest magnetic resonance experiments in a solid. He observed strong
electron spin resonance absorption in several paramagnetic salts. Applications of electron magnetic spin
resonance in solid state physics are of great importance. It is a very sensitive technique and has been
applied in many fields. The chief of these are :

1. Paramagnetic ions in crystals,

2. Unpaired electron in semi-conductors and organic free radicals,

3. Colour centres, and radiation damage centres,

4. Ferro and anti-ferro magnetic materials.

1.2 AIM OF THE EXPERIMENT

To determine the Land g-factor using Electron Spin Resonance.

1.3 APPARATUS
ESR setup which includes Helmholtz coils, R.F. oscillator and the test sample(which in our case was
diphenyl-picryl-hydrazyl (DPPH)) and in addition, a cathode ray oscilloscope (CRO).

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 2

THEORY AND WORKING FORMULA

2.1 BACKGROUND
1
Consider unpaired non interacting electron electrons. Each of which are having spin 2 and having a
magnetic moment . The hamiltonian can be witten as:

H = M. ~ = gB 1 S.
~ B ~ B
~ (2.1)
h
where,
B = 2m eh
= 5.74 104 eV T 1 is known as Bohr Magneton.
~ = h ~
S (~ are the pauli matrices).
2
g is the Land g factor.
In general the electron can have orbital angular momentum as well. So the total angular momentum
becomes,

J~ = L
~ +S
~

with eigen value "j" that goes from (l-s) to (l+s). The general expression for Land g factor is given as :

j(j + 1) + s(s + 1) l(l + 1)

g =1+
2j(j + 1)

For l = 0, it takes value of 2 as j = s.

Conventionally, the static magnetic field is assumed to be pointing along the z axis, which modifies the
above equation to
H = M. ~ = gB 1 S~z .B
~ B (2.2)
h
1
Let us now consider an atom which has an electronic ground state with total angular momentum j = 2
3
and an excited state with j = 2 .

6
 There is only a single transition which can be induced by the
absorption of radiation of frequency 12 = ( E2 E
h
1
) As the energy
does not depend on the angular momentum states, the ground
state is doubly degenerate corresponding to eigenvalues ms =
1 of Sz the excited state is quadruply degenerate corresponding
2
to eigenvalues + 23 , + 12 , 21 , 32 of Sz . If one now applies a
magnetic field B along the z-axis, each of the angular momentum
states acquires a different energy. The ground state energy level
thus splits into two sublevels and the excited state level into four
sublevels. This is called Zeeman splitting. Now instead of a
single transition of frequency 12 = ( E2 E
h
1
) many transitions
of frequencies close to 12 are possible. Experimentally this is
seen as a splitting a single absorption or emission line into several
closely spaced lines.This is called Zeeman effect. However there
are now transition possible between sublevels too (of the same Figure 2.1: Zeeman splitting
electronic energy level).This phenomena gives rise to electron
spin resonance(ESR)

2.2 ELECTRON SPIN RESONANCE

As ESR invloves transitions only between the sublevels of one energy level, we will not bother about the
Hamiltonian of the atom/molecule which gives us the energy levels. We will only worry about the part of
the Hamiltonian which is the result of the applied magnetic field B, which gives us the sublevels.
Our real system (DPPH) has just one unpaired electron. so,

B
H0 = gB Sz (2.3)
h
In addition we have an electromagnetic field of frequency in the direction perpendicular to B (here Bz )
.This AC field lies in x-y plane.The time-dependent Hamiltonian can thus be written as

H = H0 + V cos(t) (2.4)

The electromagnetic field is supposed to be very weak compared to the applied static field B, and so one
can use time-dependent perturbation theory to study this problem. The states that we will use are the
eigenstates of Sz .
Sz |mz i = hms |mz i

ms = 12 here. The energy of the unperturbed states are :

B
gB Sz |mz i = m |mz i
h

where, m = gB Bh ms .
In time-dependent perturbation theory, we know that the time-dependent interaction can cause transition

7
between various |mz i. The transition rate is given by Fermi Golden rule.

2
W12 = | h2| V |1i |2 (2 1 h)
h
Assume 2 > 1 .
Also the selection rule also ensures that transition happens only when ms =1.
Also the probability of finding an electron in the excited state after a time t ,subjected to a proper initial
condition is given by,
12
P (t) = sin2 (t)
12 + (0 )2
p
where = 12 + (0 )2
12
After long enough time the absorbed energy is propotional to 12 +(0 )2
.
This is generally small. Unless 0 = .
The behaviour of a paramagnetic substance in a magnetic field will depend on the interaction of the
particles with one another and with the diamagnetic particles. There are mainly two types of interactions.

(a) Spin - Spin: In which the spin interacts with a neighbouring spin but the total energy of the spin
system remains constant.

(b) Spin - Lattice: In which the electron spin interact with entire solid or liquid, transforming energy
from the spin system to the lattice which act as a thermal reservoir. As a matter of fact it is the
spin-lattice interaction that makes possible the observation of energy absorption from the radio-
frequency field when the resonance frequency is reached.

Two opposing processes take place in ESR. The radio frequency field tends to equalise the population of
various levels and the spin lattice interaction tends to restore the Boltzmann distribution by conversion of
the energy absorbed from the radio-frequency field into heat.

2.3 RELAXATION AND SATURATION

The process in which the electron return from an excited state to the ground state or relax back to the
ground state is known as relaxationand the time taken by the process is called the relaxation time.First, the
energy is absorbed from the radio frequency magnetic field and the equilibrium is established inside the
spin system. The time taken by this process is known as the spin-spin relaxation time and is a measure
of the rate at which magnetic energy can be distributed within the spin system though total energy is
conserved. Secondly, an exchange of energy occurs between the spin system and the lattice. The time
taken is known as the spin lattice relaxation time and is a measure of the rate of transfer of energy from
the spin system to the lattice.

In optical spectroscopy of the relaxation time is usually very short ( 108 sec) so that the relaxation
time does not impede the absorption rate. In radio frequency, on the other hand, typical relaxation times
are in milliseconds or longer and the spin do not have time to relax if the energy is supplied at a faster
rate. This situation is called the Saturation State. In other words, no additional energy is absorbed, if the
radio- frequency field power is increased beyond certain level.

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2.4 LINE WIDTH AND THE SPIN-SPIN AND SPIN-LATTICE
INTERACTIONS
The effect of the spin-spin interaction is to slightly shift the exact position of energy level of any individual
spin in the external field. This energy shift clearly depend on the relative orientation and distance of the
spin and thus is different for each spin, resulting in apparent broadening of the energy level.The effect of
the spin-spin interaction is to slightly shift the exact position of energy level of any individual spin in the
external field. This energy shift clearly depend on the relative orientation and distance of the spin and thus
is different for each spin, resulting in apparent broadening of the energy level 1
T0 , where T 0 is spin-spin
relaxation time. If the spin-lattice interactions are not weak the spin lattice relaxation time T will also be
introduced.In general case, however, the absorption line width may be estimated as
1 1
0
+
T T

2.5 WORKING FORMULA

Magnetic field at the centre of the Helmholtz coil is
32n
H= I = KI gauss
10 125a
Where I is the current in amperes and other symbols have their usual meaning.
n = number of turns in the coil (7.7 cm).
a= radius of the Helmholtz coil (500).

The peak to peak magnetic field will be Hpp = 2 2H.
Now if P is the maximum deflection (in division of CRO) and 2Q is the distance between the peaks then
magnetic field for either resonance is,
Hpp
H0 = Q (ingauss) (2.5)
P
Now our final equation,
h0
g= (2.6)
0 H0
Now = 0.927 1020 erg/gauss
h = 6.625 1027 erg.sec.

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 3

EXPERIMENTAL SET UP AND BASIC CIRCUIT

3.1 BASIC CIRCUIT

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. The sample is kept inside the tank coil of the oscillator, which in turn, is placed
in the 50 Hz magnetic field generated by the Helmholtz coils. At resonance, i.e. when the frequency
of oscillation becomes equal to frequency corresponding to the energy splitting of the sublevels, the
oscillator amplitude registers a dip due to the absorption of power by the sample. This obviously, occurs
periodically four times in each complete cycle of the supply voltage of the magnetic field. The result is an
amplitude modulated carrier which is then detected using a diode detector and amplified by a chain of
three low noise, high gain audio-frequency amplifiers to suit the input requirement of any oscilloscope.
Highly stabilized and almost ripple free power supply for the above circuit is obtained using an integrated
circuit regulator.

Figure 3.1: Block diagram of the circuit

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3.2 RF oscillator
It is a transistorised radio frequency Oscillator suitable for the determination of resonance frequency. The
power to it is provided from the ESR Spectrometer through a cable.

Frequency range : 9.5 MHz - 18.0 MHz

Accuracy : Better than 0.5

3.3 Test Sample

A test sample, Diphenyl Picryl Hydrazyl (DPPH) is placed in a plastic tube, which itself is in the induction
coils. This increases the filling factor to the maximum. DPPH is a free radical and widely used as a
standard for ESR measurements.

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 4

OBSERVATION AND DATA ANALYSIS

In our experiment we needed to calculate "g" value (Land g-factor) of a given sample. For that at first
we used the method based on a determination of the change in a load factor of the oscillatory circuit due
to paramagnetic loss.This is the Zavoiskys technique. At first we fixed a certain frequency, then we set

Figure 4.1: Line Sketch of the Resonance Peaks

a current value and adjusted the phase of the two signal. After setting the phase difference to zero, we
counted P ,which is the maximum deflection (in division of CRO) and 2Q ,which is the distance between
the peaks. After that we changed the current step by step and accordingly calculated P and 2Q value.Then
1
we plotted I vs Q. From the slope we calculated the g factor. We have done this calculation for for several
frequencies. The observational data are given below.

4.1 OBSERVATION 1
For this our frequency was 0 = 15.7M hz and P = 6.2 divisions .

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4.1.1 TABLE

Table 4.1:
SL no Current(I) (amps) Q (divisions)
1 0.15 1.5
2 0.17 1.3
3 0.191 1.15
4 0.209 1.05
5 0.233 0.9
6 0.252 0.85

4.1.2 GRAPH
1
From the above data we plotted I vs Q.

Figure 4.2: Q vs 1/I

4.1.3 CALCULATION
From the graph we get the slope as 0.219. Now using the (2.5) and (2.6), we calculated the value of g as

g = 1.9232

4.2 OBSERVATION 2
For this our frequency was 0 = 17.1M hz and P = 6.2 divisions .

13
4.2.1 TABLE

Table 4.2:
SL no Current(I) (amps) Q (divisions)
1 0.149 1.6
2 0.169 1.45
3 0.192 1.25
4 0.212 1.15
5 0.229 1.05
6 0.25 0.95

4.2.2 GRAPH
1
From the above data we plotted I vs Q.

Figure 4.3: Q vs 1/I

4.2.3 CALCULATION
From the graph we get the slope as 0.24. Now using the (2.5) and (2.6), we calculated the value of g as

g = 1.9114

4.3 OBSERVATION 3
For this our frequency was 0 = 18.5M hz and P = 6.2 divisions .

14
4.3.1 TABLE

Table 4.3:
SL no Current(I) (amps) Q (divisions)
1 0.153 1.7
2 0.172 1.55
3 0.19 1.4
4 0.21 1.25
5 0.234 1.15
6 0.25 1.05

4.3.2 GRAPH
1
From the above data we plotted I vs Q.

Figure 4.4: Q vs 1/I

4.3.3 CALCULATION
From the graph we get the slope as 0.26134. Now using the (2.5) and (2.6), we calculated the value of g
as

g = 1.899

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4.4 RESULT
Now we got the results as :

Table 4.4:
FREQUENCY(MHz "g" VALUE
15.7 1.9232
17.1 1.9114
18.5 1.899

Avarage value of g is = 1.9112 .

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 5

ERROR ANALYSIS

5.1 ESTIMATION OF ERROR

From (2.5) and (2.6), we can actually estimate the error formula. The formula is given below:

dg d(IQ) d(IQ)
log(g) = log(H0 )+constants log(g) = log(IQ)+Constants = dg = g
g IQ IQ

We can get the error in slope(i.e. IQ) from the graphs.After calculating the errors we get the errors as
follows :

Table 5.1: Error estimation

FREQUENCY(MHz "g" VALUE ERROR
15.7 1.9232 0.0184
17.1 1.9114 0.0079
18.5 1.899 0.0145

Also the relative error is

2 1.9112
=( 100)% = 4.646%
1.9112

5.2 SOURCE OF ERROR

The main source of error in this experiment comes from the sensitivity of the instruments. The electronics
circuit it self has some internal error which we can not take into account.
At the resonance frequency we get a lorenzian type fuction which has a non zero "FWHM". Ideally we
should get a dela function at the resonance frequency. But we did not get that. This is because the electron
never lies in a fixed energy level. It lies within a band of energy which has several frequencies(basically
frequency band). So, the resonance frequency it self has some error in it.

17
 6

DISCUSSION AND CONCLUSION

In this experiment we had to determine the Lande g factor of a paramagnetic substance(DPPH). We have
calculated the value as g = 1.9112 . We have also determined the relaxation time of electron using the
absorption curve. The calculation is given below:

Calculation of Relaxation time We can calculate the relaxation time (T2 ) of electron from the line
width of the absorption spectrum. The line width is basically FWHM of a peak(full width at half maxima).
Let Blocal be the FWHM of a spectrum. Then the formula for relaxation time is given below:

Et h

and

E = gB B

So,
h
T2 t = (6.1)
gB B
The graph of fitted absorption line spectrum with fitted parameters is given below.

18
 Figure 6.1: Fitted absorption spectrum

The FWHM is

= 5.095 104 T.
Blocal = 5.095 104 T.

So from 6.1 we get the relaxation time as

h
T2 t = .
gB Blocal
6.626 1027
T2 = sec. = 1.16 104 sec.
1.9112 9.27 2 1021 5.095 104

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