Electron Spin Resonance Spectroscopy

Soumik Ghosh (11MS007)

Satyajit Roy (11MS063)
Rishav Khare (11MS034)
Sayandip Dhara (11MS016)
DPS 4th year

Objective
To find out the 'g' value for electron using 2,2-Diphenyl-1-picrylhydrazyl (DPPH), (free radical,
95%) as a sample by ESR spectroscopy.
Theory
'Resonance' is a widely studied phenomenon both in classical as well as quantum physics.
The classical concept of a strong, effective coupling of interacting oscillators that occurs when
they share an identical frequency of oscillation. Electron Spin Resonance or ESR (also known as
Electron Paramagnetic resonance) is such a spectroscopic technique that makes use of unpaired
electron in the system under observation.
The phenomenon of magnetic resonance can be explained using classical picture of
magnetic moment and applied eld interaction. A particle with a magnetic moment placed in a
uniform magnetic field of intensity H0 will precess around H0 with an angular Larmor frequency
0 , where;
w0 = g(e/2me)H0
g, or the Land g-factor, depends on the state of the electron in the atom and is given by :
g = 3/2 + {S(S+1)-L(L+1)}/2J(J+1)
In case of anions in a crystal, the electronic behaviour is modified by the environment and
the g-factor may differ from the Land g-factor. This effective g-factor is also known as the
spectroscopic splitting factor. The theoretical value of the Land g-factor for an electron is very
close to 2 (The actual value of the g-factor changes for different particles used).
Now let us introduce an additional weak magnetic eld oriented in the xy plane and
rotating about the z axis (assuming Larmor precession along the z axis) with an angular frequency
1. As a result there will be an interaction between the precessing moment and the external field.
If the frequency 1 is different from 0, the angle between the field H1 and the magnetic moment
will continuously change so to average out their interaction will to zero. However, if 1 is equal
to 0 the angle between and H1 is maintained and net interaction is effective. If we look at the
system in a reference frame that is rotating about the z axis with the angular velocity 0 then the
spin will appear to make an angle =(90
0
-) with H1 and according to the previous argument will
start to precess (in the rotating frame) about H1.

This corresponds to a "nutation" and a consequent change of the angle which implies a change
in the potential energy of the particle in the magnetic field. The change in is the classical analogy
to a transition between sublevels with different m. We see that such transitions may take place
only if the rotating field has an angular frequency 1 = 0. Now suppose that the intrinsic spin
angular momentum of the electron S couples with the orbital angular momentum of electron L
to give a resultant angular momentum J. If no external field is applied on the system, the states
with different values of ml and ms are degenerate. But, on application of external magnetic field
(say H0), the J+1 magnetic sublevels are split by equal energy difference 4E, such that,
4E = g0H0
Where 0 is the Bohr's Magneton.
Now let us consider a situation where the particle is subjected to a perturbation by an alternating
magnetic field with a frequency 1 such that the quantum h1 is exactly the same as the difference
between the levels 4E, and the direction of the alternating field is perpendicular to the direction
of the static magnetic field. Then there will be induced transitions between neighboring sublevels
according to the selection rules 4m = 1 for magnetic dipolar radiation. The condition for
resonance is, therefore given by:
4E = g0H0 = hv0 = hv1
Then the g-factor can be easily calculated by:
g = hv0/0H0
The sample used to carry out the experiment is 2,2-Diphenyl-1-picrylhydrazyl (DPPH) (free radical,
95%). The chemical structure of the sample is given below.

Working Formula
Magnetic field at the center of the Helmholtz Coil is given by :
H = 32nI/(10a125) Gauss
where, `n' is the number of turns in the Helmholtz coil.(n=500)
a is the radius of the Helmholtz coil.(a =7.7 cm)
I is the current (in amp) flowing through the Helmholtz coils.
Now the peak to peak field is given by:
HPP = 22H gauss
From this the magnetic field for resonance is given by:
H0 = Q.HPP/P = 2232nQI /10125aP Gauss
Now for resonance the condition we obtained earlier is :
4E= g0H0 = h0
or, g = h0/0H0
where, 0 is the resonance frequency.

Experimental Results and Analysis



For Resonance frequency 0 = 14MHz
P = 132 V

I (mA) 2Q
102 84
112 76
122 68
131 64
143 56
152 52
164 48
174 48
184 44
195 40
204 40




Corresponding Graph





For Resonance frequency 0 = 16MHz
P = 132 V
I (mA) 2Q
101 84
112 76
125 68
139 60
151 56
163 52
170 48
188 48
199 44
210 40











For Resonance frequency 0 = 18MHz
P = 132 V
I (mA) 2Q
102 84
112 76
123 68
135 64
148 56
160 52
174 48
186 44
196 44














Calculation of 'g' factor
The Planck's constant h = 6.625x10
-27
erg-s
The value of 0 = 0.927x10
-20
erg/Gauss
1. For Resonance frequency 0 = 14MHz
From the slope of the graph,
QI = 4.56315 V-Amp
The resonance frequency is given by,
H0 = (2232nQI)/(10125aP) =5.70 Gauss
The Value of 'g' is
g = h0/0H0 =
6.62510
27
1410
6
0.92710
20
5.70
= 1.755
Thus calculated value of 'g' is =1.755
2. For Resonance frequency 0 = 16MHz
From the slope of the graph,
QI = 4.17 V-Amp
The resonance frequency is given by,
H0 = (2232nQI)/(10125aP) =5.217
The Value of 'g' is
g = h0/0H0 =
6.62510
27
1610
6
0.92710
20
5.217
= 2.191
Thus calculated value of 'g' is = 2.191
3. For Resonance frequency 0 = 18MHz
From the slope of the graph,
QI = 4.3768 V-Amp
The resonance frequency is given by,
H0 = (2232nQI)/(10125aP) =5.47
The Value of 'g' is
g = h0/0H0 =
6.62510
27
1810
6
0.92710
20
5.47
= 2.35
Thus calculated value of 'g' is = 2.35
Result
Thus the value of 'g' factor obtained for three frequency values 14 MHz ,16MHz and
18 MHz are 1.755,2.191 and 2.35 respectively.
Discussion
Thus we have carried out the experiment and the obtained value of 'g' is quite
satisfactory. The value of 'g' determined using QED is 2.002319 which is quite in
range of our experimentally obtained values. While carrying out the experiment,
four things we should keep in mind first :

1. The ESR setup must be shielded from external magnetic field or electric
field sources that interfere with the magnetic field used in the experiment.

2. High currents (~200 mA) should not be allowed to pass through the
helmholtz coil for a long time. This may cause unnecessary heat and
thereby damage can occur.

3. If the peaks do not coincide on the x-scale, the sinusoidal wave form of
the mains voltage should be checked which may be distorted due to overloading
of the main line due to other heavy gadgets working on the same
line.

4. While finding the resonance frequency, the resolution of the X channel
should be kept very low so that no peak can be observed. This will help
us to detect the beat patterns very easily.