Essence of Electron Spin Resonance

&
Nuclear Magnetic Resonance

Electron Spin Resonance (ESR) :

Electron spin resonance deals with the magnetic moment of lone electrons. This is a useful tool to
study electronic structures of paramagnetic materials (unpaired electrons), free radicals, metal com-
plexes etc. The phenomenon is attributed to spin angular momentum and corresponding magnetic
moment possessed by the single electrons. Let the electron with charge e has rest mass me . Intrinsic
angular momentum of electron be Sh̄. Then the ratio of magnetic moment (µs ) to the intrinsic angular
momentum bears a relation which depends on electronic charge and mass.

µs eh̄
= −ge (1)
Sh̄ 2me
where, ge is a dimensionless quantity and is known as Landé g factor. Electron’s angular momentum
is quantized in units of h̄. We all know that, experimental observables are magnitude of angular
momentum and magnitude of its projection along a preferred axis (Sz ) (this can be observed by
applying magnetic field along a particular direction).
√
q 3 1 1
S = (s(s + 1)) = h̄; f ors(electronspinquantumnumber) = h̄Sz = ms h̄; ms = ± (2)
2 2 2
In case, the system has a large number of electrons, the total spin will be vector sum of all the
individual spins. The residual spin for some of the systems is given below :
S = 1/2 especially for radicals
S = 1 for biradicals and triplets
S > 1 for some of the transition metals

Let us consider a system with single unpaired electron. Since, the spin of electron is 1/2, therefore
ms = ±1/2 and the multiplicity (2S+1) = 2, therefore, there are two ms level giving rise to a doublet.
So, the external magnetic field breaks the degeneracy in ms states, i.e; in absence any magnetic field
both the ms states have same energy. This lays the foundation of ”Zeeman Effect”. The interaction
energy of magnetic moment due to the field (magnetic field along z axis) is given by :

∆E = ∆(µ.B) = ge µb B = ge γh̄B (3)

eh̄ e
where, µb = 2m e
is the Bohr Magneton and γ = − 2m e
is the electron magnetogyric ratio. The value
of ge is determined to be 2.00. Above relation shows a single energy level gets split in to two levels
and the energy of the levels vary linearly with applied field. Therefore, if a microwave frequency worth
ν is incident on the sample and the resonance criteria is satisfied the wave will get absorbed and it
turn we observe an absorption peak at the resonance frequency. As the field is varied, the resonant
frequency also varies linearly. So, if landé g factor is known one can determine the Bohr Magneton and
vice-versa. A representative diagram is shown in Fig.1.
Nuclear Magnetic Resonance (NMR) :

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 ( ms = +1/2)

∆Ε = µ Β = h ν
Ε

Unpaired electron spin

(ms = −1/2)

Figure 1: Representative plot to show the splitting of an electronic spin state in to in presence of
applied magnetic field.

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 Similar to the magnetic moment and angular momentum possessed by electrons, a nucleus does have
magnetic
p moment and angular momentum. The angular momentum (SI ) whose magnitude will be SI
= sI (sI + 1) is generated by coupling of spin and orbital angular momenta of protons and neutrons.
A nucleus with spin I can assume 2I+1 spin orientation characterized by quantum number mI which
can acquire values varying from [ -I, -(I-1), ........, (I-1), I]. Interestingly the magnetic quantum number
states remain degenerate unless and until an external magnetic field is applied. Therefore, the energy
of substates in presence of magnetic field along z direction :

∆EmI = ∆(µ.B) = gI µN mI B = ge γI h̄B (4)

Here, the symbols have exactly the same meaning as in case of electron except for now the parameters
have to be calculated for a nucleus. Similar to ESR, whenever a wave of energy incident on the material
in presence of magnetic field, if the condition of resonance is satisfied,i.e; the energy carried by the
probing wave equals the energy difference between the corresponding multiplets, absorption takes place.

A point of concern is that, the nucleus is surrounded by a cloud of electrons which generate an internal
magnetic field that opposes the applied magnetic field and therefore, a correction term is introduced
in the magnitude of external field. This phenomenon is called Chemical Shift.

Exercise :We talked so much about angular momentum and magnetic moment of electrons. In the
text books one can find classical as well as quantum treatment of the phenomena. But with time we
learn that any magnetic process can only be discussed in the framework of quantum mechanics though
approximate results have been derived in the context of classical theory. Can you logically think about
the context ?

Exercise :We will next see that for ESR we use a magnetic field of around 3 mT whereas NMR uses
300 mT. Can you think of quantitatively why is this so ? [Hint : Try to calculate the values of Bohr
Magneton and Nuclear Magneton]

Exercise :We talked about ESR and NMR separately. But we know that when we refer to an atom
that means we are talking about electron, proton and neutron all together as an entity. Therefore, is
there a possibility that we actually observe the composite effect of NMR and ESR or they are individu-
ally observed in samples concerned ? [Hint : You can think of in terms of Hyperfine Structures.]

1 ESR cum NMR set up

Apparatus :

• ESR / NMR probes (see Fig.2)

• One pair of magnetic coil which can generate around 3 mT of magnetic field.

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Figure 2: ESR probe with samples. Taken from lab manual of the company www.3bscientific.com/esr-
and-nmr

• A control Console (see Fig.3)

• Power supply (12V, 50/60Hz)

• DPPH (Diphenyl Picryl Hydrazyl) sample for ESR and another test sample (see Fig.4 for the
structure of DPPH)

• A strong magnet worth 300 mT for NMR measurements (see Fig.5)

• Samples for NMR measurements : Glycerine, Polystyrene, Teflon and a test sample.
A composite set up with all the ingredients is shown in Fig.6. A schematic diagram of experimental
set up is also shown in Fig.7. A real life assembled set up for NMR measrement is shown in Fig.8.
Procedure

• Set up the coils (electromagnet) in such a way that the arrows should point away from the
observer.

• The coils are set over rings.

• Connect the coils to the ports shown as Coils at the back of Console.

• Connect the channel one and channel two for CRO or DSO to the signal and field out terminals
on the console. Set the voltage range for field out at 100 mV and for the signal out at 200 mV.

• Insert the DPPH sample holder at the appropriate slot.

• The magnetic field is shown on the DSO screen as a Triangular Waveform. It signifies that with
time the field increases to a certain value and drops down and thereafter it again triggers. The
cycle continues.

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Figure 3: The console for the set up where one can vary the frequency to attain the resonance condition.
Taken from lab manual of the company www.3bscientific.com/esr-and-nmr

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 Figure 4: The structure of DPPH.

Figure 5: Strong Magnet with NMR probe along with the samples for NMR measurement. Taken from
lab manual of the company www.3bscientific.com/esr-and-nmr

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Figure 6: Set up for ESR/NMR measurrements. Taken from lab manual of the company
www.3bscientific.com/esr-and-nmr

Detector

Microwave Generator Analysis

Amplifier
System

Attenuator Microwave Cavity

Sample

Magnetic Poles Magnetic Poles

Figure 7: Schematic Diagram of experimental set up of ESR / NMR Measurement.

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Figure 8: A live set up with all the components assembled for NMR measurement.

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 • For DPPH sample, set the frequency around 50 MHz. Be careful to see that the LED (sensitivity
knob) on the console blinks once in a second.

• One can now see a prominent peak at the signal out channel. Adjust the channel waveforms in
a way as soon in Fig.10.

• Measure the value of output voltage (UR ) at the junction where it intersects the slant increasing
curve of magnetic field. One can use the option ”Cursor” on DSO to pin point the position of
intersection. From this value one can extract the magnetic field value.

BR = 3.47UR mT /V (5)

• Now vary the frequency and keep on measuring (UR ). This would help us in calibrating the
system for magnetic field value in terms of frequency. We would plot a graph between Magnetic
field and frequency. From the straight line plot (a demo plot is shown in Fig.??) we can deduce
slope. Here we can apply the energy difference relation we discussed initially :

µb
ν = ge BR (6)
h
J
where, µb = 9.28 × 10−24 T and h = 6.626×10−34 Js.
You need to find out the graphical error to estimate in uncertainty in the slope and hence in the
value of g determined.

• All the above steps should be repeated for the testing sample.

• For experiments on Nuclear Magnetic Resonance, we need to reassemble the set up by incorpo-
rating a permanent magnet with high magnetic field along with the electromagnetic coils.
Exercise :You can see metallic strips are attached on both the magnetic poles on the outer
surface. Do you know the purpose of these strips?

• Rest of the processes are same. Here we have three known samples as mentioned in the section
”Apparatus”.

• Resonant frequencies for different samples would be in range as mentioned below:

Glycerine (1 H) 12.854 MHz

Polystyrene (1 H) 12.854 MHz
Teflon (19 F) 12.100 MHz

• Screenshot of DSO display with Glycerine and Polystyrene sample for NMR measurement is
shown in Fig.??

Inference

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 Figure 9: Output waveforms at DSO with DPPH for ESR Measurements.

• The value of Landé g factor for electron is .......................±............(with DPPH)

• The value of Landé g factor for electron is .......................±............(with test sample)

• Resonance frequency for Glycerine in NMR measurement ......................

• Resonance frequency for Polystyrene in NMR measurement ......................

• Resonance frequency for Teflon in NMR measurement ......................

• Resonance frequency for Test Sample in NMR measurement ......................

Post Lab Questions and Take Home Messages

1. Do you think, NMR and MRI are same processes?

2. In the given experiment we carried out the observations at room temperature. What will happen
to the measurements if the temperature is lowered?

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Figure 10: Magnetic field is plotted as a function of frequency in ESR experiment with DPPH.

Figure 11: Output waveforms at DSO with Glycerine for NMR Measurements.

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Figure 12: Output waveforms at DSO with Polystyrene for NMR Measurements.

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Figure 13: Set-up of the experiment with power supply unit (DC power supply) for the electromagnets
(on the left), NMR apparatus (in the middle) and NMR operating unit (on the right).[Taken from
Didactic Manual]

2 NMR set up
The NMR apparatus consists of the probe which sits on an electromagnet. This creates a homogeneous
magnetic field (main magnetic field). Arranged vertically to this, an induction coil placed around the
sample generates a field alternating at a high frequency. Now, either the strength of the magnetic field
or the frequency of the alternating field can be varied until resonance occurs with the sample. When
resonance occurs, the sample absorbs energy. Therefore, an additional amount of energy is necessary
to maintain the alternating field. This signal, the NMR signal, is measurable with an oscilloscope, for
example. This version of NMR spectroscopy is referred to as the continuous wave (CW) method.
The required equipment is shown in Figure 13 and the components of the NMR apparatus in Figure
18. Following connections are to be made as per the manual from DIDATIC.

• Mount both 10 A coils onto the U-core. These provide the electromagnets.
• In order to construct the NMR probe, push the small modulation coils from both sides over the
pole shoes up to the measuring chamber (max. gap between the coils: 35 mm, align in parallel).
• Place the NMR probe (with the sample opening pointing upwards) evenly onto the U-core and
fix it in place with fixing clamps (not too tightly).
• Electrical set-up (see figure 15)
– Connect the 10 A coils in series to the DC power supply.
– Connect the modulation coils in series to the MODULATION COILS output of the NMR
supply unit.

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Figure 14: Construction of the NMR apparatus and parts of the NMR probe.[Taken from Didactic
Manual]

Figure 15: Electrical set-up of the NMR apparatus (schematic diagram).[Taken from Didactic Manual]

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 – Connect the NMR probe to the PROBE input. Do not lengthen the short BNC cable.
– Connect the NMR SIGNAL output to the vertical deflection channel (Y) and the ∆B SIG-
NAL output to the horizontal deflection channel (X) of the oscilloscope.

PS : Above connections are already. Do not disconnect or try to modify. You

are requested to cross verify the connections with the schematic diagram given
in the manual
– How to record data for a given sample :
∗ Take the tube filled with a given sample, say, glycerine (Glycerine (C3O3H8) contains
8 protons per molecule and the sample is liquid). Move the O-ring of the sample tube
so that the sample is immersed roughly up to the centre of the measuring chamber.
CAUTION : DO NOT TRY TO PUSH THE SAMPLE HARD AS IT CAN
DAMAGE THE ELECTROMAGNET CORE
∗ Connect the oscilloscope according and operate it in X-Y mode.
∗ On the NMR supply unit, set the HF amplitude to minimum and the frequency and
modulation amplitude to maximum. Choose FAST SWEEP and switch on the NMR
supply unit.
∗ Increase the HF amplitude as slowly as possible until the LED lights up.
∗ Set a frequency of around 18.5 MHze (for better adjustment see the results given in the
figures below).
Note: With some frequencies or magnetic fields, spontaneous oscillation
occurs in this frequency range through the presence of many electrical ap-
pliances. This is not the NMR signal.
∗ On the DC power supply, slowly increase the voltage and therefore the magnet current
through both 10 A coils until an NMR signal appears in the oscilloscope. Note: On
increasing the magnet current, the NMR signal appears as a brief deflection. Alterna-
tively, with the defined current strength of around 3 A, the frequency on the NMR unit
can be slowly reduced.
∗ Vary the HF amplitude slowly and optimise the NMR signal.
∗ Shift the NMR signal to the centre of the oscilloscope screen by varying the magnet
current or the frequency and reduce the modulation amplitude at the same time. Adjust
the phase of the modulation voltage so that the NMR signals for both half-waves of the
modulated magnetic field coincide. Note: The NMR signal can drift away in some cases.
If this happens, regulate again if necessary.

For the convenience of setting up the instrument for different samples by different batches of students,
tuned set up parameters along with the waveform of the DSO are shown below :

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Figure 16: Results og Glycerine

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Figure 17: Results of Teflon

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Figure 18: Results of Polysterene

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