Electron Spin Resonance Spectroscopy: Calculating the Landé

g-factor for a free electron

Name: Rahul Devarakonda
Roll number : 2018/UG/019

Contents
1 Apparatus 2

2 Introduction 2

3 Theory 3

4 Summary of the formulas used 4

5 Procedure 4

6 Observations and Results 5

7 Conclusion 5

Figure 1: Representation of the intrinsic, extrinsic and total angular momentum.

1
 Abstract
In this experiment, our aim is to find the value of the Landé g factor for an electron subjected to a
perturbation by an external alternating magnetic field.

1 Apparatus
1. Basic circuit: ESR spectrometer (model-105), the circuit consists of critically adjusted radio frequency
oscillator having a frequency range of approximately 10-17MHz.
2. Phase shifter: this can compensate the undetermined phase difference which may be introduced in the
amplification stages of the spectrometer and oscilloscope.
3. 50 Hz sweep unit: For modulation with low frequency magnetic field, a 50 Hz current flows through the
Helmholtz coils.
4. Power supply: The Helmholtz coils power consists of step down transformer (220 to 35V AC).
5. Helmholtz coils: There are two coils exactly alike and parallel to each other, connected so that current
passes through them in the same direction. The number of turns in each coil n=500, diameter of winding
a= 7.6cm and separation of the coil is 7.7cm.
6. Sample: the test sample, Diphenyl picryl Hydrazyl (DPPH) is placed in a plastic tube inside the R.F coil.
7. Oscilloscope: The Oscilloscope for the observation of ESR resonance has:
Screen diameter : 12.5 cm
Vertical amplifier sensitivity : 50 m V/cm

2 Introduction
Electron spin resonance (ESR) is a useful tool for investigating the energy absorption spectra of many materials
with unpaired electrons (paramagnetic materials). The molecule will have an intrinsic magnetic dipole moment
due to the unpaired electron. ESR is a purely quantum mechanical effect. It relates the interaction of an external
magnetic field to an electron’s magnetic moment, which is a result of its intrinsic spin. Since the spin of an
electron may either be up or down, so may its magnetic moment. This implies that, in the presence of an
external magnetic field, one spin state will be higher in energy than the other. The spin with a moment pointing
in the direction of the external field is lowest in energy. These states have an energy E, as
1
E = ± gµB B (1)
2
Where µB is the Bohr-Magneton and B is the external magnetic field. Hence, the change in the negative spin
state to the positive spin state is given as
∆E = gµB B (2)
At commonly attainable magnetic field strengths the corresponding energy lies in the radio-frequency (RF)
regime. Where the general expression for the energy of a photon applies and we have
∆E = h(ν1 − ν2 ) (3)
An unpaired electron responds not only to a spectrometer’s applied magnetic field B0 , but also to any local
magnetic fields of atoms or molecules. The effective magnetic field Bef f experienced by an electron is thus
written Bef f = B0 (1 − σ), where σ includes the effects of the local fields. Hence, the resonance condition can be
written as
hν = ge νB Bef f = ge νB B0 (1 − σ) = gνB B0 (4)
ge is the Landé g-factor, where we have used σ and g to get the last form.
Eq.(4) is used to determine g in this experiment by measuring the field and the frequency at which resonance
occurs. If g does not equal ge , the implication is that the ratio of the unpaired electron’s spin magnetic moment
to its angular momentum differs from the free electron value. Since an electron’s spin magnetic moment is
constant (approximately the Bohr magneton), then the electron must have gained or lost angular momentum
through spin-orbit coupling. Because the mechanisms of spin-orbit coupling are well understood, the magnitude
of the change gives information about the nature of the atomic or molecular orbital containing the unpaired
electron.

2
3 Theory
This study analyzes the almost free electron in Diphenyl Picryl Hydrazil also called DPPH in short. A nitrogen
pair in the center of the molecule has a trapped electron with no orbital angular momentum. The magnetic
moment of the molecule is determine only by the spin moment of the valence in the N- bridge. DPPH has
been studied extensively with ESR because of its ability to absorb free radicals. A modulated frequency and a
varying current flowing through the Helmholtz coil is used to determine the g-factor of DPPH as compared to
the accepted theoretical value.

Figure 2: Diphenyl Picryl Hydrazil(DPPH)

Coming back to the theory of the experiment, let us consider a particle having a magnetic moment µ ~ which is
placed in a uniform magnetic field of intensity B~0 . Then the moment µ
~ will precess around B~0 with the angular
Larmour frequency
e
ω0 = g B0 (5)
2mc
Where g is the Landé g-factor. Let us proceed to the quantum picture of elementary magnetic resonance. Suppose
that the intrinsic angular momentum of the electron S ~ couples with the orbital angular momentum L ~ to give a
~ ~ ~
resultant J = L + S. We know, that J + 1 magnetic sublevels labelled by the magnetic field is given by

∆E = gµB B0

between adjacent sublevels.

The correct quantum mechanical value for the Landé g-factor is
J(J + 1) + S(S + 1) − L(L + 1)
g =1+ (6)
2J(J + 1)
Also, if a particle is subjected to perturbation by an alternate magnetic field with a frequency ν1 such that the
quantum hν1 is exactly the same as the difference between the levels, ∆E and if the direction of the alternating
field is perpendicular to the static magnetic field, then there will be induced a transition between neighbouring
sublevels according to the selection rules ∆m = ±1 for the magnetic dipole radiation.
Therefore by the resonance condition

∆E = gµB B0 = hν0 = hν1 (7)

Where ν1 is the resonance frequency. The requirement is identical with the classical condition ω1 = ω0 . Thus, to
find the Landé g-factor, we use Eq.(7)
hν0
g= (8)
B0 µ0
The magnetic field in the Helmholtz coil is
32πn
B= √ I G (9)
10 125.a
Since the current measured is in rms, the magnetic field is also rms. The peak to peak magnetic field (after
placing the values of the constants given) will be,
√
Bpp = 2 2B = 165.25  I GA−1

Now, to check for resonance, we use the RF-oscillator (Oscilloscope) and determine approximately the set value
of the frequency. The distance between the two peaks is denoted by 2Q.

3
 Figure 3: The distance between the peaks being meausured

So,
QI
B0 = 165.25 × (10)
P
Where P is the deflection in the CRO X-plate. Hence, the Landé g-factor is calculated as

hν0 P
g= × (11)
µB QI  165.25

4 Summary of the formulas used

To calculate the Landé g-factor, we use the formula

hν0 P
g= ×
µB QI  165.25

Where 2Q =Distance between peaks and P = deflection in the CRO X-plate.

5 Procedure
1. We increase the horizontal sensitivity of the Oscilloscope to the maximum within the linear range.

2. We then obtain the best possible peaks by varying the frequency , detection level and vertical sensitivity of
the Oscilloscope, keeping the current at 150 mA.
3. Now, keeping the frequency fixed, we vary the current through the coils and measure the corresponding
horizontal seperation between the two peaks (2Q) after adjusting the phase.

4. We then plot a I1 vs Q graph which is expected to be a straight line. We then calculate the g-factor from
the slope of the graph.

4
6 Observations and Results
Sample: DPPH
Frequency: 14.02 MHz
Total X-Plate Deflection P : 70.0 mm
Table 1: For the Landé g-factor

Serial No Current(I)(in mA) 2Q (in mm) 1/I (in A−1 ) Q (in mm)
1 125 34 8.00 17.0
2 150 28 6.67 14.0
3 175 24 5.71 12.0
4 200 21 5.00 10.5
5 225 19 4.44 9.5
6 250 17 4.00 8.5
7 275 15 3.64 7.5
8 300 14 3.33 7.0

Using the data given, we plot the following 1/I vs Q graph:

Figure 4: 1/I vs Q plot

The slope of the linear plot is QI = 2.13 ± 0.03 mm.A−1 .

Thus, placing h = 6.625 × 10–27 erg.sec, µB = 0.927 × 10–20 erg.G–1 , ν0 = 14.02 MHz and P = 70.0 mm in
Eq.(11), we get;
hν0 70 mm
g= × = 1.99 ± 0.02
µB (2.13 ± 0.03 mm.A−1 ) × 165.25

7 Conclusion
The landé g-factor is found to be g = 1.99 ± 0.02