BITS-Pilani K.K.

Birla Goa Campus, Physics Department

PHY F344: Advanced Physics Laboratory

Electron Spin Resonance (ESR)

Material supplied:
1) ESR spectrograph with sample, 2) Oscilloscope

Purpose of the Experiment:

1) Investigating electron spin resonance in di-phenyl picryl hydrazyl (DPPH) sample.
2) To determine the value of Landé g factor using electron spin resonance.

Basic Methodology:
Material with unpaired spin moment is placed in a magnetic field. This results in the
precession of the moment with Larmor frequency. A small high frequency (MHz)
magnetic field is applied perpendicular to main field. The frequency of the oscillating
field is kept fixed and the main magnetic field is slowly oscillated (at 50 Hz) to have
electron spin resonance four times per cycle. Landé g factor is calculated.

Theory:

Electron Spin Resonance (ESR), also known as Electron Paramagnetic Resonance

(EPR) or simply Electron Magnetic Resonance (EMR, like NMR), was discovered by
the Russian physicist Eugene (Yevgeny) Zavoisky in 1944, as a part of his Ph.D.
thesis work (Thesis title: Paramagnetic absorption in perpendicular and parallel
fields for salts, solutions and metals). It was also developed almost concurrently by
the British Physicist Brebis Bleaney at Oxford University, UK. In 1992, Bleaney
received the International Zavoisky Award "for his contribution to the theory and
practice of electron paramagnetic resonance of transition ions in crystals". ESR is a
phenomenon found in systems that possess electron with unpaired spin. It is a very
sensitive technique and has been applied in many fields. The chief of these are:
Paramagnetic ions in crystals, unpaired electron in semi-conductors and organic free
radicals, colour centres, and radiation damage centres, ferromagnetic and anti-
ferromagnetic materials.

The magnetic moment of an electron due to its spin is given μB = eℏ/2me (the Bohr
magneton), where me is the mass of the electron. We now begin with a classical
description of the motion of electron spin in an external applied magnetic field B =Bo
z, where z is a unit vector. μB will precess about the static field B with an angular
frequency ω = γB and this frequency is called the Larmor frequency and γ is called
the gyromagnetic ratio. γ = geμB/ℏ, where ge is the Landé “g” factor. It is 1 for purely
orbital motion and 2.0023 for electron spin. Hence the precession frequency for an
electron is fE = ω/2π = γB/2π = gμBB/h. Substituting numerical values one gets fE =
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 BITS-Pilani K.K. Birla Goa Campus, Physics Department
PHY F344: Advanced Physics Laboratory
2.802 MHz/G. The corresponding value for proton (in NMR) is fP= 4.26 kHz/G). This
value is much lower than in ESR because of the higher mass of the proton. So one
can observe ESR at a given frequency for a field which is two-three orders of
magnitude smaller than required for NMR in the same frequency range.

We saw in the previous paragraph that an unpaired electron when placed in a

magnetic field precesses about the field with a natural frequency ωe = γB. This
precession produces an oscillatory magnetic moment in any direction normal to the
applied field, which can interact with an oscillatory magnetic field, BE cos ωEt, which
is also normal to the applied field. The interaction has a marked effect on the
precession of the electron only when ωE is close to the natural frequency of electron
precession ωe so that one gets resonance absorption of the oscillating magnetic field.
This energy from the field is used by the electron to flip from precessing in the
direction of the external field to precessing against the external field. Thus, when the
resonance condition is fulfilled, i.e. when ωE = ωe = γB, the component of the spin
along the steady field can be flipped even by oscillatory fields whose amplitude BE
<< B. This effect is known as “Electron spin resonance".

In quantum mechanical picture, we

can visualize this as follows. If the B applied
B = 0, S= ½ ms = - ½
unpaired electron has spin S= 1/2 ,
then an external DC field Bo applied ℏωe = γℏB
to it will spilt the level into two,
separated from the main level by ± ms = + ½
½γℏB. The separation between the
two levels will be γℏB = ℏωe. An alternating magnetic field with frequency ωE applied
perpendicular to the static magnetic field will cause a transition between the two lines
provided ωE = ωe = γB.

The population of the electrons in the two states is determined by the Boltzmann
distribution {N=No exp (-E/kT) }. For example, for fE = 10 GHz, at room temperature
(T~300 K), the ratio of the population in upper and lower states is 0.998. This
difference is quite small but < 1. That is the reason why we always have resonance
absorption of the oscillating field into the system.

As seen earlier, for ESR, fE = 2.802 MHz/G. So the resonance frequency for
electronic system in magnetic fields of 3,000 to 10,000 gauss lies ~109 Hz (3 cm
microwave region). Of course one can always change the resonance frequency ωe by
changing B, but in most cases it is advantageous to use as large a magnetic field as
possible since the energy quanta absorbed are then larger and the resonance is
correspondingly stronger. However, for demonstration purpose, it is much cheaper

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 BITS-Pilani K.K. Birla Goa Campus, Physics Department
PHY F344: Advanced Physics Laboratory
to have an electronic megahertz source, using magnetic fields of few gauss, as done
in the present experiment. Also, in ESR experiments, unlike in NMR experiments,
the oscillator frequency is kept constant and the magnetic field is oscillated slowly.

Di-phenyl picryl hydrazyl (DPPH) will be used as the

sample material. It has several chemical names and its
structure is shown in the adjacent figure. It has a stable
free radical (one unpaired nitrogen bond, shown as a
dot over N in red circle), and it is a standard material
used for ESR demonstration.

Theory related to the experimental procedure:

As mentioned earlier, in the ESR experiments, Bmax

Magnetic field B
instead of adjusting the RF frequency, one B o
ωe= γBo
keeps it fixed and the magnetic field (which is Time
supposed to be static) is oscillated slowly (at 50 ωe= γBo
-Bo
Hz in the present experiment). During each
oscillation, when the field amplitude B reaches 1 2 3 4
a value Bo corresponding to the resonance
frequency (fE =γBo/2π =gμBBo/h or ωe= γBo), there is resonance absorption of the RF
signal, and this will happen four times in one cycle. If the RF absorption is displayed
on the Y axis and the magnetic field oscillating (at 50 Hz) on the X axis, one will see
four spikes corresponding to these four resonance absorption peaks.

It must be noted here that had the RF field been circularly polarized, the absorption
would have occurred only in one half cycle, giving rise to two peaks instead of four.
However, since the RF field is linearly polarized, it can be seen as composed of right
circularly polarized (RCP) and left circularly polarized (LCP) fields. One of the two
polarizations gets absorbed resonantly twice in each half of the cycle and hence one
gets four resonance absorption peaks. Q

When one adjusts the phase difference

between X and Y inputs, one can get the first
two peaks (1 & 2) overlapping and the last two
(3 & 4) overlapping, so that one sees only two
peaks. Let P be the total extent of the horizontal
trace on the oscilloscope (measured in terms of
divisions on the oscilloscope, as absolute
P
length will not matter) and let Q be the
separation between the two peaks. P will correspond to the peak to peak magnetic
field (2Bmax) and Q will correspond to 2Bo.
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 BITS-Pilani K.K. Birla Goa Campus, Physics Department
PHY F344: Advanced Physics Laboratory
For a current I flowing in a Helmholtz coil pair, the magnetic field produced by it at
the mid-way point (where the sample is placed) is given by B = (8/5√5)[μoNI/R ] =
0.716 [μoNI /R ]. For the coils used in the experiment, radius R=7.7 cm, and N=500.
So we have B = (58.4 G/A) I. Since measured current is the r.m.s. value, the peak
current will be √2 times the measured current. Hence Bmax= (82.625 G/A) Irms. Thus
P, which corresponds to 2Bmax will correspond to (165.25 G/A) Irms. Also, Q
corresponds to 2Bo. Thus P/Q = 2Bmax/2Bo. Hence Bo = (82.625 Irms) (Q/P) gauss,
where Irms is the measured current flowing in the coils (in A). It may be noted that as
P remains unchanged with change in coil current, Q decreases with increase in the
current. From the slope of Q vs/ 1/ Irms, one can get the value of Bo. [Slope = BoP].

Since fE = g μB Bo / h, where h is the Planck’s constant (6.626x10-34 J-s) and μB =

9.274x10-28 J/G, one can calculate the value of g from the expression g = fE h /(μB Bo).

Experimental setup:

Original equipment supplied by: Scientific Equipment & Services Pvt. Ltd., Roorkee, India.

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 BITS-Pilani K.K. Birla Goa Campus, Physics Department
PHY F344: Advanced Physics Laboratory
Experimental procedure:

1) Make the connections as shown in the diagram on the previous page.

2) Switch on the ESR Spectrometer power supply.

3) Switch on the “H-COIL” power and set the current in the Helmholtz coils at 100
mA.

4) Connect the terminals marked “X”, “Y” and “E” to the oscilloscope. “E” is for
earthing and “X” and “Y” are horizontal and verticals scans of the oscilloscope.

5) On the spectrometer power supply, set “Frequency” and “Phase” knobs centred,
and turn the “Sensitivity” knob fully clock-wise.

6) Four peaks should be seen on the oscilloscope. Adjust the “Frequency” and
“Sensitivity” knobs and the oscilloscope trigger level to get four sharp peaks with
good signal-to-noise ratio.

7) Now adjust the “Phase” knob to coincide the four peaks to two, as much as
possible. {Peak amplitudes may not exactly match}

8) Now pick up the RF oscillator connected to the “9 V” socket and bring it within 1
foot of the Helmholtz coils.

9) Tune the RF frequency of this oscillator by looking at the oscilloscope. On either

side of the correct frequency, in its close vicinity, you should be able to observe
beats. Note down this frequency. This is the frequency of the source.

10) Note down the distances P (Total length of the trace) and Q (distance between
the two peaks).

11) Repeat measurement of Q for various values of the r.m.s. current (100 mA to 250
mA in steps of 25 mA)

12) Tabulate your data as follows: P = … mm; fE = …. MHz

-1
Current I [A] Q [mm] Q/P 1/ I [A ] Bo = (82.625 I) (Q/P) [G] g = 0.7144 fE Bo.
0.100
0.125
..
0.250

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 BITS-Pilani K.K. Birla Goa Campus, Physics Department
PHY F344: Advanced Physics Laboratory
13) Calculate the average value of the Landé g factor.

14) Plot Q/P vs. 1/I [A-1]. This should be a st. line as (Q/P) =Bo /(82.625 I)

15) Calculate the value of the Landé g factor from the slope of this line.

16) Repeat the experiment for another value of resonant frequency (f2).

Results:
1) Average value of Landé g factor for the first frequency (f1)
2) Plot of Q/P vs. 1/I [A-1] for the first frequency (f1)
3) Value of Landé g factor from the slope of this line.
4) Average value of Landé g factor for the second frequency (f2)
5) Plot of Q/P vs. 1/I [A-1] for the second frequency (f2)
6) Value of Landé g factor from the slope of this line.
7) Reasons for deviation, if any, of the above four results from g = 2.0023.

General information:

1) Although Landé g factor does not change as such, any magnetic field of nearby
atoms has an effect on the effective magnetic field seen by the electrons. This
change in the effective field due to nearby atomic magnetic fields is usually
clubbed into the g factor. Thus any deviation of g from Landé g factor provides
information about the magnetic environment of the atoms under investigation.

2) ESR measurements not only give information about the existence of unpaired
electrons, but also provided information about quantity, type, environment etc.

3) ESR instruments provide the only means of selectively measuring free radicals
non-destructively and in any sample phase (gas, liquid or solid).

4) ESR is actively being used in pharmaceutical and agricultural basic research, and
is widely used in clinical and medical fields, such as cancer diagnosis.

5) Hyperfine interaction of the nuclear spin with the electron spin gives rise to
multiple EPR lines. For example, for a radical having M equivalent nuclei, each
with a spin of I, the number of EPR lines expected is 2MI + 1.

END
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