The Electron Spin Resonance of DPPH

By Joseph Dotzel
With Jedidiah Riebling
Date: 2/18/2014
Abstract
In this paper, we consider the science of Electron spin resonance. We set out to
find three things in this experiment. We were to determine the magnetic field as a
function of the resonance frequency, to determine the land splitting factor, and the find
the width of resonance. Using our sample of DPPH, we took measurements of both DC
current and Magnetic field strength over a range of frequencies from 15 MHz to 100
MHz. We also took measurements of the line width of resonance at 50 MHz. Using
these measurements we were able to obtain a value of for the land splitting
factor, and a value of for the width of resonance. The accepted values for
each of these factors fell within the error bars of our experimental values.
Introduction
In this experiment we are using phenomena of electron spin resonance. Since
its discovery by the Russian scientist Zavoisky in 1944, electron spin resonance (ESR)
has proven useful in observing crystalline structures and has many applications in the
fields of physics, chemistry, and medical fields.
1

Electron spin resonance is performed by observing the absorption of radiation of
a paramagnetic sample placed within an oscillating magnetic field. The magnetic field
induces a change in the spin state in the electrons of the sample, causing an emission
of photons, which can be observed as a change in the magnetic field.
2

In order to perform this experiment a special paramagnetic substance is required.
The substance that is used is 2,2-diphenyl-1-picrylhydrazyl or DPPH. It is a free radical
that is relatively stable and contains an unpaired electron on the nitrogen chain (see fig
1).This electron contributes almost zero orbital angular momentum or is quenched.
This means that the interaction of this electron with the magnetic field will be entirely
from the spin of the electron.
2


Figure 1 DPPH
3
This experiment will have three goals. The first is to determine the magnetic field
B
0
as a function of the resonance frequency. The second will be to determine the land
splitting factor g. The last is to find the width of resonance B
0
. The rest of this paper
will cover the theory, experimental method, the data, and the results of the experiment.

Theory
The theory of electron spin resonance is based around the angular momentum of
the free electron in the DPPH. Since the electron is quenched, we can assume the
orbital angular momentum to be zero. The spin angular moment whose magnitude is
given by
(1)
where the spin quantum number s= and is Plancks reduced constant. With this we
can determine the magnetic moment of the spin given by

(2)
Where

is the Bohr magneton and g is the land splitting factor or g-

factor. Since we are considering the electron in DPPH a free electron with no orbital
angular momentum the g-factor should be g=2.0023. This comes from the Dirac
function and quantum electrodynamics.
2

Using equation (2) we can determine the energy of an electron at a given spin
state using the equation

where B is the magnetic field.

As shown in figure 2 the two possible energy states will be

and

and the change in energy is given by Equation 3 where h is planks constant

and v is the resonance frequency.

(3)
For the purposes of this experiment equation 3 will be used to solve for our
experimental land splitting factor g.

Figure 2: electron splitting in applied magnetic field
3

In order to determine the magnetic field used in equation 3, a measurement can
be taken using a tesla meter or it can be determined by measuring the DC current using
an ammeter. Using the current and the following equation

(4)
where

is the permeability of free space, N is the number of turns of the Helmholtz

coils, R is the radius of the Helmholtz coils, and I is the current passing through the
Helmholtz coils the magnetic field can be determined. For our experiment we will use
both methods.
In addition to the magnetic field and g factor, the width of resonance B o is also
worth exploring. For the purposes of this experiment, the width of resonance is a
representative of the uncertainty of energy splitting E. The uncertainty principle states
that you cannot know the exact location and momentum of an electron at the same
time. As your measurement of one becomes more precise the other becomes less
precise. It can be applied as

where T is the lifetime of the energy state. Using equation 3 we can get the relation of

(5)
This equation theoretically proves that the width of resonance is independent of the
frequency.
For the purposing of this experiment the width of resonance will be determined
by taking measurements of the line width at resonance , the Voltage of modulation
U
mod
, and the AC current of the system I
mod
. The line width can be converted to a
voltage by using the following conversion factor where is the line width.

(6)
From this, a current can be found by using the following equation

(7)
After obtaining this the width of resonance can be found by inserting this value into
equation 4. Having discussed the mathematics and physics of the experiment, the
experimental method can be explained.
Experimental Method
To perform the experiment the equipment was set up as in figure 3, described in
more detail in the lab manuel
4
, with the Helmholtz coils at a distance of R apart (figure
4). Measurements were then made of the DC current and magnetic field at resonance
for a range of frequencies for each RF probe.

Figure 3 Pasco SE-9634 Electron Spin Resonance Apparatus
4
Figure 4 Helmholtz coil
setup
4
In order to get a sufficient amount of results across the spectrum of frequencies 3
RF probes were used and measurements of the DC current were taken using a
ammeter . For the large probe 8 measurements were made at frequencies between 15-
35

. For the medium probe 11 measurements were made between 25-75

. Finally
for the small probe 9 measurements were made between 60-100

, resulting in 28
measurements being made. These ranges were chosen to cover the range of
measurable frequencies for each RF probe.
In order To find the resonance at each frequency, the DC current was adjusted
so the resonance pulses on the oscilloscope occurred when the AC current to the
Helmholtz coils was zero (fig 5). The current was then measured using an ammeter.

Figure 5 oscilloscope display screen at resonance. Figure 6 Measurement of Half Width
The measurements for the magnetic field were made using a tesla meter for each
frequency at the location of the sample. The magnetic field was then calculated using
equation 4 to be compared to the measured values.
In order to determine the land splitting factor g, the relationship between the
frequency and magnetic field was plotted and from that the slope of the curve fit was
obtained. This slope value

can be used with equation 3 in order to solve for g.

Finally, to obtain the width of resonance, a measurement of the line width of the
resonance peak is needed. To do this the oscilloscope was switched to x-y mode at a
frequency of 50

and the line width was measured at the half minimum (Fig6) of the
peak. A measurement of the AC current was also taken using the ammeter. Using the
line width, AC current, and the voltage U
mod
the width of resonance can be determined
using equations 7 and 4.

Data and Analysis
The first set of data (Table 1) shows the measured Magnetic field vs. the
calculated magnetic field. The data shows figures that are very comparable to each
other. Most of the values fall within or just outside the error bars. This is a good sign that
the experimental equipment and procedure are being used correctly.

Table 1: Measured and calculated magnetic field Table 2: Frequency vs
magnetic field

Table 2 shows the frequency, magnetic field, and current measurements
collected during the experiment. From the data in table 2, a positive correlation between
frequency and magnetic field becomes apparent. As the frequency is increased from 15
MHz to 100 MHz over the three RF probes the magnetic field increases from 0.80 mT to
Current amps Measured Magnetic Field mT Calculated Magnetic Field mT
error = 0.01 error = 0.03 error = 0.02
0.45 0.80 0.85
0.39 0.70 0.74
0.38 0.68 0.72
0.49 0.88 0.93
0.55 0.98 1.04
0.58 1.00 1.1
0.66 1.18 1.25
0.70 1.30 1.33
0.47 0.83 0.89
0.60 1.06 1.14
0.69 1.28 1.31
0.81 1.53 1.54
0.87 1.64 1.65
0.91 1.72 1.73
1.03 1.92 1.96
1.09 2.00 2.07
1.23 2.35 2.34
1.30 2.41 2.47
1.42 2.61 2.7
1.14 2.12 2.17
1.27 2.38 2.41
1.31 2.40 2.49
1.40 2.65 2.66
1.52 2.87 2.89
1.57 2.95 2.98
1.71 3.16 3.25
1.77 3.38 3.36
1.86 3.57 3.53
Frequency MHz Measured Magnetic Field mT
error = 0.1 error = 0.03
15.0 0.80
18.0 0.70
21.0 0.68
24.0 0.88
27.0 0.98
30.0 1.00
33.0 1.18
36.0 1.30
25.0 0.83
30.0 1.06
35.0 1.28
40.0 1.53
45.0 1.64
50.0 1.72
55.0 1.92
60.0 2.00
65.0 2.35
70.0 2.41
75.0 2.61
60.0 2.12
65.0 2.38
70.0 2.40
75.0 2.65
80.0 2.87
85.0 2.95
90.0 3.16
95.0 3.38
100.0 3.57
3.57 mT. By plotting frequency vs. magnetic field (fig 6), we find that this relationship is
linear in nature. Applying a linear curve fit gives the equation of
and an R value of 0.99664 showing that this is a very strong fit for the data.

Figure 6: Frequency vs. Magnetic field strength
Using the slope of the curve fit and equation 3, we found the land
splitting factor . This is a very good result considering that the accepted
value of g for a sample of DPPT is 2.0023. The accepted value fell well within the error
bounds of our experimentally determined g value.
Using measurements of the line width at resonance and equations 6 and
7, the width of resonance was determined to be . The accepted
value for the width of resonance ranges from 0.15 to 0.81 based on the solvent in which
the substance has been recrystalized in
1
. Our experimentally found value falls well
within this range of values.
The error for this experiment starts with the precision of the equipment we used.
From there, the error was calculated using the standard error propagation.
2 2 2
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Of note, the error of the measured magnetic field was taken from the fluctuations we
saw from the tesla meter rather than the precision of the device.
Conclusions
This experiment set out to find three things, to find the magnetic field as a
function of the resonance frequency, to find the land splitting factor g and to determine
the width of resonance. This experiment was a success as it managed to accomplish all
of these. Furthermore the accepted values for the land splitting factor and the width of
resonance fell well within the error bars of our experimentally obtained values.
Considering the results there was little uncertainty from the experiment, however one is
notable. The tesla meter had a lot of fluctuations while taking measurements. This was
minimized by including this in our error calculations. Other sources of uncertainty would
be room temperature and humidity of the room affecting the equipment. In conclusion,
this experiment helps demonstrates the science and concept behind electron spin,
which is an important part of examining molecular and crystal structures in the field of
physics, chemistry, and medicine.



References
"Electron Spin Resonance at DPPH." LEYBOLD Physics Leaflets. LEYBOLD
DIDACTIC GMBH Web. 28 Feb. 2014.
<http://www.ifsc.usp.br/~lavfis/BancoApostilasImagens/ApRPE2_Leybold/Param
agneticRessonance_P6262_ESpinDPPHLabwriteup.pdf>.
"Electron Spin Resonance." New York University Department of Physics. Web. 18 Feb.
2014. <http://physics.nyu.edu/~physlab/Modern_2/ElectronSpinResonance.pdf>.
Griffith, Dave. Instruction Manual and Experiment Guide for the PASCO scientific Model
SE-9634, 9635, and 9636. Roseville, CA: PASCO Scientific, 1995. Print.
Kaur, Parminder, Paul Oyala, and Yu Guo. "EPR: Theory." - Chemwiki. N.p., n.d. Web.
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<http://chemwiki.ucdavis.edu/Physical_Chemistry/Spectroscopy/Magnetic_Reso
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