Running head: electron spin resonance

Electron Spin Resonance

Png Wen Han, 130041, School of Physics

Author Note
This work is submitted to Lecturer in charge of this experiment, Dr Yoon Thiem Leong by 22th March 2017.
Correspondence concerning this report should be addressed to Png Wen Han, School of Physics, University
of Science, Malaysia, 11800 USM, Penang, Malaysia. Contact: WENHAN@student.usm.my,
 [Title Here, up to 12 Words, on One to Two Lines] 2

Abstract

This report presents an analysis on electron spin resonance at diphenyl picryl hydrazyl (DPPH),
mainly focus at determining the resonance magnetic field as a function of the selected resonance
frequency, the g- factor of DPPH. The analysis is validated experimentally. DPPH is a free radical
chemical, thus the unpaired electrons is least likely to be influenced by their orbital motion. It is possible
to obtain a good value for the free electron gyromagnetic ratio from measurements on a free radical.
This allow the calculation of the Lande g factor. We used a ESR basic unit from Leybold in this
experiment. This unit generate a RF field inside the copper coil. The 3 different copper coils give 3
different ranges of frequencies. For each type of plug-in coil, the resonant current I 0 as a function of
frequency v. Data of I 0 vs v was tabulated with ranges between 15 MHz -130MHz. The magnetic
field of the Helmholtz coils can be calculated from the current I through each coil. The data of magnetic
field B 0 vs frequency v was tabulated. The g-factor was calculated from the data. Their reference
values are g=2.0036 . The error of g factor was obtain using least square fit method.

KEYWORD: electron spin resonance, diphenyl picryl hydrazyl (DPPH)

Nomenclature

Magnetic dipole movement

B Magnetic Field

S spin angular momentum

E Potential energy
g Lande g factor
v frequency
gyromagnetic ratio
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Theory

Electrons have magnetic dipole movement, due the spinning charge on their axis.

Under an external magnetic field B , a free electron will then acquire a potential energy
given by:

1.1
E= . B

The relationship between magnetic moment and the spin angular momentum S can be
written as:

1.2
= S

, where is the gyromagnetic ratio. is to be e/2m, if a uniform sphere with

homogenous charge distribution. Real electrons have a larger magnetic moment than simple
model predicts, and the discrepancy is often written in terms of the Lande g factor:

1.3
g >1
e/2 m

Assuming the magnetic field B to be pointing in the z-direction, the potential energy is:
E= z B z 1.4
S z Bz

Quantum mechanics state the S z can only have two values:

1.5
S z =
2
The potential energy will only have two values:
Bz 1.6
E=
2
The difference in two energy is then:
E= B z 1.7

Corresponding the energy difference, incident photon on the lower energy sate electron get
absorbed, inducing the electron to flip its orientation: this phenomenon is electron spin
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resonance, since the photon energy is equivalent to the potential energy difference, then equation
1.7 can be rewrite in term of frequency of the incident radiation:
Bz 1.7
v=
2

A chemical free radical is one unpaired electron per molecule and these substances are
paramagnetic, these unpaired electrons are least likely to be influenced by their orbital motion.
Thus, it is possible to obtain a good value for the free electron gyromagnetic ratio from
measurement on the free radicals. This allow the calculation of Lande g factor (Pitre). In this
experiment, we are using Diphenyl picryl hydrazyl (DPPH) as free radical chemical.

Figure 1 Chemical structure of 1,1-diphenyl-2-picryl-hydrazyl (DPPH)

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Method

The experiment setup is illustrated as Figures 2 and 3. (ESR Basic Unit, ESR adapter, ESR Control Unit)
a) The Helmholtz coils was set up parallel to each other at an average distance of 5.0 cm
(equal to the average radius r).
b) The Helmholtz coils was connected in parallel to each other and in series with the
amperemeter to the ESR control unit.
c) The EST basic unit was connected to the ESR control unit via the 6- pole cable.
d) The output y of the ESR control unit was connected to channel l of the two channel
oscilloscope and the output X to channel II via BNC cables.

Figure 2 Experimental setup for electron spin resonance at DPPH.

Figure 3 Arrangement of the Helmholtz coils viewed from above.

Procedure
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1. The plug-in coil 15-30 MHz (the biggest one of the three coils) was put on and the DPPH
sample was inserted so that it is in the center.
2. The ESR basic unit was switched on and set up so that the plug-in coil with the DPPH
sample was in the center of the pair of Helmholtz coils (see Fig. 5).
3. The resonance frequency was set at = 15 MHz (potentiometer on top of the basic unit).
4. The modulation amplitude I~ was set to the middle.
5. The phase shift was set to the right (potentiometer Phase).
6. Two-channel operation was selected at the oscilloscope.
7. Dual on time base 2 ms/cm Amplitude I and II 0.5 V/cm AC
8. The button on the control unit was used to switch the display of the control unit to A=,
showing the value of I=. The equidirectional field of the Helmholtz coils was slowly
enhanced with the current I= until the resonance signals are equally spaced (see Fig. 3).
9. The oscilloscope was switched to XY operation, and the phase shift was set so that the
two resonance signals coincide (see Fig. 2).
10. The direct current I= was varied until the resonance signal was symmetric. A modulation
current I~ was selected as small as possible.
11. The direct current I= was read through the pair of Helmholtz coils together with the
resonance frequency , creating Table 1. The resonance frequency was increased by 5
MHz, and the new resonance condition was adjusted by increasing the direct current I=.
12. The current was measured and recorded.
13. The high frequency was continue increased in steps of 5 MHz (use the plug-in coil 30-75
MHz for frequencies greater than 30 MHz and the plug-in coil 75-130 MHz (the smallest
one) for frequencies greater than 75 MHz) and the measurements was repeated.
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Data and Analysis

Data tabulation of current value for each current
In Table 1, the current through the series-connected Helmholtz coils I mod in the case of
resonance is listed as a function of the frequency of the alternating high frequency field.
/ MHz I/A Plug-in coil
17.1 0.157 Big
20.0 0.172 Big
25.0 0.205 big
30.0 0.243 Big
35.0 0.307 medium
40.0 0.347 Medium
45.0 0.384 Medium
50.0 0.411 Medium
58.6 0.475 Medium
60.1 0.512 Medium
65.0 0.548 medium
70.0 0.613 Medium
74.1 0.616 medium
80.0 0.634 small
85.0 0.647 Small
90.0 0.648 Small
95.0 0.654 Small
100.0 0.645 Small
105.0 0.645 Small
110.0 0.654 Small
115.0 0.683 Small
120.0 0.692 Small
125.0 0.695 Small
128.4 0.707 Small

Table 1: the current I0 as a function of the frequency of the alternating field

Evaluation
The magnetic field B of the Helmholtz coils can be calculated from the current I through each
coil:

3
B=0 . ( ) . nr . I , =4 .10
4
5
2
0
7 Vs
Am

(n: number of turns per coil, r: radius of the coils)

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I
With n = 320 and r = 5.0 cm, B= 5.75 mT. is obtained.
A
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Determining the resonance magnetic field B 0 :

In Table 2 the values calculated for the magnetic field are compiled.

/ MHz B /mT
17.1 0.90
20.0 0.99
25.0 1.18
30.0 1.40
35.0 1.77
40.0 2.00
45.0 2.21
50.0 2.37
58.6 2.73
60.1 2.95
65.0 3.15
70.0 3.53
74.1 3.55
80.0 3.65
85.0 3.72
90.0 3.73
95.0 3.77
100.0 3.71
105.0 3.71
110.0 3.77
115.0 3.93
120.0 3.98
125.0 4.00
128.4 4.07

Table 2: The magnetic field B 0 as a function of the frequency of the alternating field.

The data in Table 2 is plotted into graph as followed:

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GRAPH OF MAGNETIC FIELD VERSUS FREQUENCY

4.50
f(x) = 0.03x + 0.87
4.00 R = 0.89

3.50

3.00

2.50
Magnetic field,mT 2.00

1.50

1.00

0.50

0.00
0 20 40 60 80 100 120 140

frequency,MHz

Fig. 6 shows a GRAPH OF MAGNETIC FIELD VERSUS FREQUENCY

The slope of the straight line through the origin drawn in the plot is
v
m= =0.0286 mT / M Hz
B0
From this the g- factor follows:

B 0= ( hg ) v
B

h
m=
B g
h
g=
m B
g=2.495

the uncertainty of g is given by:

g m
=
g m
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m
g= g
m
0.000002193418986846694
g= .2.495
0.000028638477986106258

g=0.191
Therefore, the g-factor is 2.495 0.191
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Error analysis

We used Mathematica to perform all the data analysis, the Mathematica code can be found in
Appendix section. The standard error of the gradient is 2.19 x 10^-6 mT / M Hz . The r 2 value is
0.8857. This indicate each point of the graph is not seriously deviate from the assumed pattern (linearly
proportional) .The proportional relation between magnetic field and frequency of electron spin is valid

Our experimental value for g- factor is 2.495 0.191 . The experiment result is not valid as the
range of permitted g-factor value is from 2.304 2.686 , which has no theoretical value (2.0036) fall into
this range. The percentage of discrepancy is given by:

theoritical valueexperimental value

percentage of discrepancy= 100
theoritical value
2.00362 .459
100
2.0036
22.73
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Discussion

Almost a quarter percentage of discrepancy indicate some error has been occur during the
experiment. We deduced a few errors from some observations as followed:

a) The phase shift of the resonance signal became harder to compensate in smaller copper
coils.

b) The value of direct current in ESR unit box fluctuate more in smaller copper coil make
harder taking the reading

c) The increase in direct current with the increase of resonance frequency is relatively
insignificant especially from (85 MHz to 110MHz).

d) The threshold of the ESR unit box enable only direct current till at most 0.707 A only,
but theoretical speaking, it should go beyond 0.707A till a maximum value ( I > 1 A)

The errors are as followed:

a) The Diphenyl-Picryl-Hydrazyl (DPPH) is not preserve properly (not in air-seal test tube,
just warp with plastic), we believe the free radical chemical has been contaminated.

b) The central magnetic field supplied by 2 Helmholtz coils to the free radical is not
uniform.

c) The table next to our experiment carry out Hall effect experiment, this external magnetic
field cause disturbance to out experiment.

Therefore, we suggested a few precautions to minimized the error,

a) The Diphenyl-Picryl-Hydrazyl (DPPH) should be preserve properly for next use,

preferably in airtight test tube.

b) The distance between the coils should be adjust until it is equal to their radius. This
provide the most uniform magnetic fields at the center.

c) This experiment should be carry out in environment with zero magnetic field disturbance.
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Conclusion

This experiment confirm the proportional relation between magnetic field and frequency of
an electron spin. This experiment also obtains Lande g factor, g to be 2.495 0.191 with
percentage of discrepancy of 22.73%

References

.Ingram, D.J .E. Free Radicals as Studied by Electron Spin Resonance. Butterworth,London,

1958.

"ESR Basic Unit, ESR adapter, ESR Control Unit." Leybold-Heraeus, Instruction Sheet. Koln,

1986.

Pitre, John. "Electron Spin Resonance." Advanced Undergraduate Laboratory Experiment 15.

1988.
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Appendix

SetDirectory[NotebookDirectory[]];
(** provide the name of your linear data file in *.xls format *)
datafile="ESR2.xls";
(*for example, datafile="ESR2.xls"*)

(*datafile="sampel_linear_data.xls";*)
Print["The name of the data file you provide is ",datafile];
SetDirectory[NotebookDirectory[]];
txy=Import[datafile,"XLS"][[1]];
lpttxy=ListPlot[txy,AxesLabel->{
x,y}];

(*
"The best fit parameters can be obtained by using Mathematica's built-
in function 'FindFit'"
*)
ff=FindFit[txy,bb*x+aa,{bb,aa},x];
besta=aa/.ff;
bestb=bb/.ff;

"Overlap the best fit straight line on the rawdata"

Show[{lpttxy,Plot[bestb*x+besta,{x,0,130}]}]

(*"An alternative but more powerful method to find the best fit
parameters for linear function is LinearModelFit"
*)
lmf=LinearModelFit[txy,{x},x]

"The error in bestm and bestc can be retrieved from LinearModelFit

using ParameterTable"
lmf[{"BestFit","ParameterTable"}]