Electron Spin Resonance

Introduction

• Electron Spin Resonance (ESR) also known as Electron Magnetic Resonance (EMR) or Electron
Paramagnetic Resonance (EPR) is a branch of absorption spectroscopy in which radiations having
frequency in the microwave region (0.04 – 25 cm) is absorbed by paramagnetic substances to induce
transitions between magnetic energy levels of electrons with unpaired spins.
• ESR is based on the fact that atoms, ions, molecules or molecular fragments which have an odd number of
electrons exhibit characteristic magnetic properties. An electron has a spin and due to spin there is
magnetic moment.
• Since its discovery in 1944 by E.K. Zavoisky, EPR spectroscopy has been exploited as a very sensitive and
informative technique for the investigation of different kinds of paramagnetic species in solid or liquid
states.
Principle of Electron Spin Resonance (ESR)

• The phenomenon of electron spin resonance (ESR) is based on the fact that an electron
is a charged particle. It spins around its axis and this causes it to act like a tiny bar
magnet. When a molecule or compound with an unpaired electron is placed in a strong
magnetic field, the spin of the unpaired electron can align in two different ways creating
two spin states = ± ½.
• The alignment can either be along the direction (parallel) to the magnetic field which
corresponds to the lower energy state = – ½ and Opposite (antiparallel) to the direction
of the applied magnetic field = + ½
• The two alignments have different energies and this difference in energy lifts the
degeneracy of the electron spin states. The energy difference is given by:
∆ E = – = hυ = gmßB
Where,
h = Planck’s constant (6.626 x 10-34 J s-1)
υ = the frequency of radiation
ß = Bohr magneton (9.274 x 10-24 J T-1),
B = strength of the magnetic field in Tesla
g = the g-factor which is a unit less measurement of the intrinsic magnetic moment of the
electron, and its value for a free electron is 2.0023.
An unpaired electron can move between the two energy levels by either absorbing or
emitting a photon of energy = hυ  such that the resonance condition, hυ = ∆E, is obeyed.
This leads to the fundamental equation of EPR spectroscopy.
Working of Electron Spin Resonance (ESR)

• Although the equation permits a large combination of frequency and magnetic field values, the
great majority of EPR measurements are made with microwaves in the 9000–10000 MHz (9–
10 GHz) region.

• EPR spectra can be generated mostly by keeping the photon frequency fixed while varying the
magnetic field incident on a sample.

• A collection of paramagnetic centers, such as free radicals, is exposed to microwaves at a fixed

frequency.

• By increasing an external magnetic field, the gap between the energy states is widened until it
matches the energy of the microwaves.

• At this point the unpaired electrons can move between their two spin states. Since there are
typically more electrons in the lower state, due to the Maxwell–Boltzmann distribution, there
is a net absorption of energy.

• It is this absorption that is monitored and converted into a spectrum.

Instrumentation of Electron Spin Resonance (ESR)
KLYSTRONS
• Klystron tube acts as the source of radiation.
• It is stabilized against temperature fluctuation by immersion in an oil bath or by forced air cooling.
• The frequency of the monochromatic radiation is determined by the voltage applied to klystron.
• It is kept at fixed frequency by an automatic control circuit and provides a power output of about 300 milli watts.

WAVE GUIDE OR WAVEMETER

• The wave meter is put in between the oscillator and attenuator.
• To know the frequency of microwaves produced by klystron oscillator.
• The wave meter is usually calibrated in frequency unit (megahertz) instead of wavelength.
• Wave guide is a hollow, rectangular brass tube. It is used to convey the wave radiation to the sample and crystal.

ATTENUATORS
• The power propagated down the wave guide may be continuously decreased by inserting a piece of resistive material into
the wave guide. This piece is called variable attenuator.
• It is used in varying the power of the sample from the full power of klystron to one attenuated by a force 100 or more.

ISOLATORS
• It’s device which minimizes vibrations in the frequency of microwaves produced by klystron oscillator.
• Isolators are used to prevent the reflection of microwave power back into the radiation source.
• It is a strip of ferrite material which allows micro waves in one direction only.
• It also stabilizes the frequency of the klystron.
SAMPLE CAVITIES
• The heart of the ESR spectrometer is the resonant cavity containing the sample.
• Rectangular TE120 cavity and cylindrical TE011 cavity have widely been used.
• In most of the ESR spectrometers, dual sample cavities are generally used This is done for simultaneous observation of a
sample and a reference material.
• Since magnetic field interacts with the sample to cause spin resonance the sample is placed where the intensity of magnetic
field is greatest.

COUPLERS AND MATCHING SCREWS

• The various components of the micro wave assembly to be coupled together by making use of irises or slots of various sizes.

CRYSTAL DETECTORS
• Silicon crystal detectors, which converts the radiation in D.C has widely been used as a detector of microwave radiation.

MAGNET SYSTEM
• The resonant cavity is placed between the poles pieces of an electromagnet.
• The field should be stable and uniform over the sample volume.
• The stability of field is achieved by energizing the magnet with a highly regulated power supply.
• The ESR spectrum is recorded by slowly varying the magnetic field through the resonance condense by sweeping the current
supplied to the magnet by the power supply.
MODULATION COIL
• The modulation of the signal at a frequency consistent with good signal noise ratio in the crystal detector is accomplished
by a small alternating variation of the magnetic field.
• The variation is produced by supplying an A.C. signal to modulation coil oriented with respect the sample in the same
direction as the magnetic field.
• If the modulation is of low frequency (400 cycles/sec or less), the coils can be mounted outside the cavity and even on the
magnet pole pieces.
• For higher modulation frequencies, modulation coils must be mounted inside the resonant cavity or cavities constructed of a
non-metallic material e.g., Quartz with a tin silvered plating.

DISPLAY DEVICES
• In order to observe the signal a system is connected different devices can be used.
Applications of Electron Spin Resonance (ESR)

• ESR spectrometry is one of the main methods to study transition metal containing metalloproteins.
• To determine the rate of catalysis
• To know about the active site geometry
• To study denaturation and protein folding
• In studies relating to enzyme-ligand interaction 
• In Biological Systems 
• Study of Free Radicals 
• Spin Labels 
• Study of Inorganic Compounds 
• Reaction Velocities & Mechanisms 
• Study of naturally occurring substances such as minerals with transition elements, minerals with defects (e.g;
quartz), Hemoglobin (Fe), Petroleum, Coal, Rubber etc.
• Conducting Electrons
Thank You