BASICS OF ELECTRON PARAMAGNETIC RESONANCE SPECTROSCOPY

By splitting the electron spin ground state in a strong external magnetic field, we get Zeeman
resonances in the gigahertz (GHz = 109 Hz) range of the electromagnetic spectrum. The observation
of these spectral features is the basis of electron paramagnetic resonance (EPR) spectroscopy, which
is also known as electron spin resonance (ESR).

Otto Stern and Werner Gerlach had already demonstrated it in their famous experiment of 1921: a
collimated beam of silver (Ag) atoms, which are in the ground state 2S½ at room temperature (one
5s electron, the other shells are full or empty), passes parallel to the edge of the wedge-shaped pole
shoe of an electromagnet, so that the magnetic field and its gradient are aligned parallel (z-axis).
The atomic beam travels perpendicular to this direction. A homogenous magnetic field only affects
the orientation of microscopic magnetic moments µ. The inhomogeneous magnetic field, however,
applies a force in the z direction

which diverts the atomic beam in this direction. From the above equation, we get maximal
deflection with opposite sign for microscopic magnetic moments in the z and –z-directions.

z
y
Fig. 5.1 Stern-Gerlach Experiment. The cross section of the
x z
magnet, and the beam of silver atoms coming from the gas
reservoir. The beam is collimated by masks and split in the
inhomogeneous magnetic field. The detector was a cooled
glass plate to which the silver atoms stuck. The spots were
seen after chemical development.

Ag Source

According to classical laws, we should observe deflection in the direction of the gradient of the
magnetic field for random orientations of μ (except for perpendicular orientation of the dipole to
the external field). In applying the inhomogeneous magnetic field, the cross section of the atomic
beam was not even approximately continuous. Two spots instead of one were seen along the z
axis. Two conclusions could be drawn from the experiment:

1) the existence of the magnetic moment of the electrons (whose connection to the spin of the
electrons was first made in 1925 by Samuel Abraham Goudsmit and George Eugene Uhlenbeck),
and
2) the proof of two preferred directions of the magnetic moment, which were later shown in quantum
mechanics to be the magnetic quantization of the electron spins in an external field.

The Stern-Gerlach experiment was a major influence in the development of modern physics.
It created a basis for the high frequency spectroscopic methods used in the study of paramagnetic
substances. In 1938, Isodor Isaak Rabi developed molecular beam resonance. EPR and NMR
followed. NMR, is based on nuclear paramagnetism (gross selection rule), and EPR is based on
electron paramagnetism (gross selection rule).
 Basics of EPR Spectroscopy

Electromagnetic radiation may be regarded classically as coupled electric (E 1) and magnetic

(B1) fields, oscillate at same frequency at the particular energy region, perpendicular to the
direction of propagation. According to the particulate nature of electromagnetic radiation, it
can be represented as a stream of particles called photons with energy (h). These photons
have a type of spin angular momentum, whereas no mass or net electrical charge, whilst
photons travel in observable directions, always at the speed of light. When a photon is
absorbed or emitted by an electron, atom or molecule, the energy and angular momentum of
the combined (total) system must be conserved. In most spectroscopic studies, other than
magnetic resonance, it is the electric-field component of the radiation that interacts with
molecules. For absorption to occur, two conditions must be fulfilled: (1) the energy (h) of a
quantum of radiation must correspond to the separation between certain energy levels in the
molecule, and (2) the oscillating electric-field component E1 must be able to interact with an
oscillating electric-dipole (or higher) moment. Similarly, a molecule containing a magnetic
dipole may interact with the oscillating magnetic component B1 of electromagnetic radiation.
Indeed, This interaction forms the basis for magnetic resonance spectroscopy.

Much of our knowledge of the structure of molecules has been gained from the analysis of
molecular absorption spectra. Such spectral data are obtained by measuring the intensity
(transmission or absorption) versus frequency (or wavelength) of a beam of electromagnetic
radiation as it passes through a sample (matter). Spectral lines or bands in a spectrum represent
transitions between energy levels of the absorbing molecular species. The frequency (or
wavelength) of each line or band measures the energy separation of two levels. Based on enough
spectral data and some rudimentary guidance from the theory (quantum theory), one may
construct an energy-level diagram from a spectrum. Comparison of an energy-level diagram and
an observed spectrum clearly indicates that, of the many transitions that may occur between the
various levels, relatively few specifically ‘allowed’ transitions are observed. Hence the prediction
of transition intensities requires detailed knowledge of selection rules.

EPR spectroscopy method detects unpaired electrons of materials contained in a homogeneous

magnetic field using microwave radiation to establish the resonance condition that can be detected by
suitable microwave detectors. It is often called electron spin resonance (ESR) as many systems with
unpaired electrons are free radicals. electron paramagnetic resonance (EPR) is a technique used
in chemistry and physics, materials science (e.g. to characterize polymers, magnetic and conducting
materials, crystalline defects, etc.) and increasingly in biology and medicine. EPR can also be used for
magnetic resonance imaging where it has the special advantage of only detecting unpaired electrons
contained, usually, in a specific spin-labeled drug.

Electron paramagnetic spectroscopy is based on the interaction of magnetic dipole moment of an

unpaired electron with an external magnetic field B0. This interaction, called the Zeeman-interaction,
results in a splitting of the spin energy levels [ΔE = g.β.B0 (See below)] of the electron into two
different energy levels associated with the spin quantum number ms (ms = ½). The number of spins
(N) in the excited state (upper level, ms = +½), and the ground state (lower level, ms = ½) is depending
on the magnitude of the energy level separation (ΔE) besides the temperature (T), according to the
Boltzmann factor:
NUpper / NLower = e(ΔE/kT)
When the sample is exposed to an electromagnetic radiation of appropriate frequency, , the
spectroscopic transitions between the two spin levels are induced when gβB0 = h , where h is the Plank
constant.
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 Basics of EPR Spectroscopy

A material is called paramagnetic, if it has no macroscopic magnetic moment (magnetization) in the

absence of an external magnetic field, however in a magnetic field which forces the magnetization in
the direction of the field. This can be understood by imagining that the stochastically (randomly)
oriented microscopic magnetic dipole moments are aligned by the external magnetic field. Thus, for the
phenomenon of electron paramagnetism, an atomic, ionic, or molecular magnetic moment is necessary.
The existence of such a magnetic moment is the same as the existence of non-filled electron shells or
the existence of unpaired electrons. Paired electrons have the same quantum numbers n, l, m, but
opposite spin quantum numbers s = +½ and s = ½. In atoms or molecules with completely filled
electron shells (all orbitals are doubly occupied), all electrons are paired, i.e. the resulting orbit and
spin moments are zero.
Nevertheless, such particles can often be examined with EPR if they are converted to a paramagnetic
state (e.g. creation of free radicals or triplet states) transiently, for example, by irradiation with high-
energy radiation such as hard X-ray radiation or γ-ray radiation.

Typical systems that can be studied using EPR spectroscopy methods

include:
1. Free Radicals in the Solid, Liquid or Gaseous Phases. A free radical is herein defined as an
atom, molecule or ion containing one unpaired electron. (Tran- sition ions and „point‟ defects in
solids fitting this description are not normally called „free radicals‟.)
2. Transition Ions Including Actinide Ions. These transition metal ions often may have up to
five or seven unpaired electrons.
3. Various ‘Point’ Defects (Localized Imperfections, with Electron Spin Distributed over Relatively
Few Atoms) in Solids. Best known in this class is the F center, an electron trapped at a
negative-ion vacancy in crystals and glasses. Deficiency of an electron (a „positive hole‟)
may also give rise to a paramagnetic entity.
4. Systems with More than One Unpaired Electron. Excluding ions of Transition series
elements, these include:
(a) Triplet-state systems. Here the interaction between the two unpaired electrons is
strong. Some of these systems are stable in a triplet ground state but most are unstable,
requiring excitation, either thermal or usually optical, for their creation.
(b) Biradicals. These systems contain two unpaired electrons that are sufficiently remote
from one another so that interactions between them are very weak. Such a system
behaves as two weakly interacting free radicals.
(c) Multiradicals. Such species (having more than two unpaired electrons such as organic
molecular magnet systems) also exist.
5. Systems with Conducting Electrons. e.g., semiconductors and metals

The origin of the signal is therefore the electron. In fact, since many students of chemistry
are much more familiar with NMR, one way of describing EPR is as if it were NMR with the
electron as the observant nucleus. To extend this analogy a little further:

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 Basics of EPR Spectroscopy
NMR property EPR equivalent
 observe nucleus (e.g. 1H, 77Se)  one or more unpaired electrons
 magnetic dipole vs. magnetic quadrupole  ms =  ½ (i.e. resembles spin-½ nuclei)
 chemical shift (i.e. field/frequency ratio)  g-value (i.e. field/frequency ratio)
 homo-nuclear coupling  normally not seen - all electrons equivalent
 hetero-nuclear coupling (always first-order)  hyperfine splitting (always first-order)

References: Shriver, Atkins, Langford, Inorganic Chemistry, 2nd edition (Freeman, 1994) p. 606 - 608 Buttler and
Harrod, Inorganic Chemistry, (Benjamin/Cummings, 1989) p. 221-225.
J.A. Weil, J.R. Bolton and J.E. Wertz, Electron Paramagnetic Resonance, (Wiley, 1994).

1. Electron spin.
 Electron spin energy levels become distinct only when the atom is inside the magnetic field.
 The size of this energy gap is larger than for nuclear spin, and the spectroscopy takes place
in the microwave frequency range. The size of the energy gap is given by the equation:

E = h0 = gµBB0

Here g is the Landé splitting energy, usually called the "g value." This is 2.002319 for the free
electron (after incorporating the quantum eletrodynamics corrections), and the applied
magnetic field strength is in Gauss or Tesla or mT units. (1 Tesla = 10,000 Gauss.), while µB
 
is the Bohr magneton, µB = eћ/2me (9.27400949  10 27 JT 1).

B0 is the applied magnetic field (B and H are almost, but not quite interchangeable measures
of magnetic field strength (There is a fundamental difference in the definitions of magnetism
laws using cgs and SI units!).

The size of E corresponds to photon energies in the microwave region of the electromagnetic
spectrum. Thus EPR spectrometers combine microwave sources and detectors with powerful
electromagnets, in a similar manner NMR spectrometers integrate radio frequency technology
with superconducting magnets.

Page 4
 Basics of EPR Spectroscopy

mS = +1/2
E
n
e
r E
g
y

ms= 1/2

Magnetic Field

Presentation of EPR spectra

Traditional spectrometers used a detection circuitry that naturally provided a dispersion

signal. This means that the spectra appear as the “first-derivative” of the absorption peak.
Since EPR spectra often have quite broad lines, there is a distinct advantage to this
„derivative‟ type of data presentation, and for this
reason the convention has been retained.
Consider the spectrum at the right, taken from a real
sample of a heterocyclic system. The left-hand curve is
the absorption peak; the right-hand is the original
dispersion pattern! Obviously the dispersion signal is
much easier to interpret, e.g. by counting the number
of lines. Experimentally, we can also generate „the
first derivative‟ pattern of the absorption feature of
EPR spectrum by modulating the applied magnetic
field experienced by the sample.

The center of an EPR spectrum is calculated as the corresponding "g-value". This is more akin
to the chemical shift of the signals in an NMR spectrum. In virtually all cases, one species
only gives one EPR signal, hence there is normally only one g-value! The g-value of molecules
and atoms measures how far the magnetic environment of the unpaired electrons differs from
that of a free, gas-phase electron. Reference compounds such as "Fremy's salt" or DPPH are
used as the g-value reference compounds. If we compare the left-hand EPR spectrum (figure
above) with a typical 1H-nmr spectrum, we may see another important aspect of EPR: the
bands are broad w.r.t. the difference in g-value, and although the possible range of g-values is
huge, most free-radicals, in fact, exhibit very little variation in their g-value. For such
compounds, it is the rule rather than the exception to have overlapping spectra if there is
more than one compound present in a solution.

2. Hyperfine splitting
What closely relates EPR to NMR is that the electron spin energy levels are split by the interaction of
nuclear spins of attached nuclei. This results in a multi-line pattern (Multiplets), which for each set of N
equivalent nuclei gives: No. of lines = 2nI + 1 ;
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 Basics of EPR Spectroscopy
where n = the number of equivalent nuclei the electron couples to, and I = nuclear spin.

We first consider a very simple example: a deuterium atom, which of course has a single electron.

The spin of deuterium is I = 1. Looking back at the splitting induced by the magnetic field (figure below),

the effect of the hyperfine splitting is that of additional small

“nuclear magnets”. The amount of the splitting depends on the
value of I. For this simple example, the resulting splitting turns
out to be:

Critical to the appearance of the spectrum is the EPR selection rule

(the same as in NMR), which is that Ms (the change in electron
spin quantum number) = 1, while MI (the change in nuclear
spin quantum number) = 0. These transitions therefore predict a
1:1:1 triplet spectrum. This is of course the same result as that
predicted by the 2nI + 1 rule: 2  1  1 + 1 = 3.

Consider as an example the CH2OH radical for which

the EPR spectrum is:

In ESR spectroscopy alone, this splitting due to nuclear

spin multiplicity is called "hyperfine splitting". Despite
the odd name, it means nothing else than splitting in an
NMR signal!
Note that such splitting is by definitions
“heteronuclear”, i.e. between the electron and a nucleus, species with very different resonance frequencies.
When one or more of the spin-active nuclei is found to be less than 100% abundant, the spectra obtained are
superposition’s of more than one spectrum arising from the different magnetic active isotopic nuclei. Such
spectra are usually referred as exhibiting “satellite features”.

In a free radical, the unpaired electron occupies a molecular orbital and interacts with spins
from other closely surrounded electrons and nuclei. In the Following example, in an EPR
spectrum where the unpaired electron interacting with two sets of equivalent protons: 2 and
4arising from the molecules Butadiene ion in liquid NH3 is depicted below:

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 Basics of EPR Spectroscopy

Furthermore, the intensity ratio can also be predicted without developing detailed
energy-level diagrams because they follow simple polynomial expansions (Pascal‟s
triangle), as shown in the following table:

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Basics of EPR Spectroscopy

Page 8
 Basics of EPR Spectroscopy

Hyperfine interactions: electron and proton 

E = gβB0mS + amSmI ms mI
Selection rules: ∆mI = 0 , ∆mS = 1
E = h = gB0 + msmI a
Hres = h/g  ms mI a (ms = 1/2, +1/2; +1/2
mI = 1/2, +1/2) 
+1/2
E 1/2

1/2
1/2
B0 +1/2
a

h/g

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 Basics of EPR Spectroscopy

3. EPR spectra of transition metal complexes

Consider the EPR spectrum of bis(salicylaldiminato)copper(II):
63
Cu: I = 3/2, (2NI + 1) = 4, 0 4 groups of lines
HA: I = 1/2, two equivalent ones, (2NI + 1) = 3 lines times
N: I = 1, two equivalent ones, (2NI + 1) = 5 lines
Since 3  5 = 15, each group should be 15 lines!

By far the largest splitting

constant is that due to the 63Cu
nucleus (100% enriched in this
spectrum). This implies that H H
the unpaired electron due to the N O
9
d electron configuration of Cu N
2+
Cu is mostly concentrated on O H
the metal. The presence of the H
other signals implies that some
of the electron density is spread onto the ligands, but only as far as the immediate coordination
sphere.

property electron proton ratio

Rest mass me = 9.1094*1028 g mp =1.6726*1024 g 5.446*104

Charge e=  4.80286*1010 ESU e=4.80286*1010 ESU 1

Angular h/4 h/4 1

momentum
gyromagnetic γe =  1.76086  107 γn = 2.67522189  104 658.21
ratio 1 1 1 1
rad.s .G rad.s .G
Magnetic mS =  ge meS mS =  gN mNS 1836.12
dipole moment ge = 2.002322 gN = 5.5856
me = eh/4.me.c = mN = eh/4.mN.c =
9.274*1021 erg/G 5.0504*1024 erg/G

Frequency: Factor 103 larger in EPR ! (GHz instead of MHz)

Sensitivity : Factor 100 000 better than in NMR !! (10 nM instead of 1 mM ) =
much higher technical/electronics requirements, but unique sensitivity to
molecular motion
Coupling strength: Factor 1 000 000 larger in EPR ! (MHz instead of Hz)
Relaxation Times: Factor 1000 000 smaller in EPR ! (ns instead of ms)

Some basic aspects of EPR spectroscopy methods are pertinent for the understanding of the
underlying principles. These aspects will be discussed in the next session.
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 Basics of EPR Spectroscopy

In EPR, the most important parameter for the description of the spin system is the g factor. Before
we define it, we will first briefly turn to orbital and spin magnetism, in which we will go from a
classical to a quantum mechanical description.

An electron orbiting at radius r with the angular frequency  creates a current I = e/2 where the
magnitude of the elementary charge e = 1.602  10 C. In general, the magnetic moment of a
current I, which encloses the surface A, is µ = IA. With A = r2, µ = ½ er2. With the angular
momentum L = me.r2. (electron mass me = 9.109  1031 kg), we get an orbital magnetism which
depends on the angular momentum L:

For spin magnetism, we assume a rotating sphere of mass me and charge e (the axis of rotation
goes through the center of mass). We divide this sphere into infinitesimal volume elements, in
which the ratio of segment charge through segment mass is independent of segment size. We then
perform for each segment the same procedure that we used for an electron in a circular orbit and
add all their contributions to the dipole moment. We get a magnetic moment dependent on the
electron spin S, analogous to the above equation for orbital momentum:

where S is the s pin angular momentum of the electron.

Due to the quantization of the angular momentum, we need the orbital angular momentum
quantum number l and the spin quantum number s for the magnitude.

| | √ ( ) | | √ ( )

The components in the direction of the external magnetic field in the z-direction are

Lz = lzħ  mlħ and Sz = szħ  msħ

There are 2l+1 magnetic quantum numbers for the orbital magnetism

ml = l,l +1, ..., l1, l (5.06)

and only two magnetic quantum numbers for electron spin magnetism

ms = +½, & ½.

Correlation Between Magnetic Moments & Angular Momenta

The magnetic moment and angular momentum are proportional to each other, in
both classical and quantum mechanics. An analog of an orbital magnetic dipole is a
classical particle of mass m and charge e, rotating with velocity V (speed v ) in a
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 Basics of EPR Spectroscopy

circle of radius r, taken to lie in the xy plane. Associated with the circulating electric
current i is a magnetic field equivalent to that produced by a point magnetic dipole.
Such a dipole has a moment i and is normal to the plane, where  = r2 is the area
of the circle. The effective electrical current i (charge flow per unit time) is ev/2r.
The magnetic moment points along the direction z perpendicular to the plane of the
circle and is given by

The sign choice depends on the direction of rotation of the particle. Here l z is the
orbital angular momentum of the particle about the axis z. The proportionality
constant, γ = e/2m is called the gyromagnetic ratio (or sometimes the magnetogyric
ratio) and has units C.kg1 = s1.T1. The proportionality constant, γ, converts the
angular momentum l to magnetic moment, μ. More generally, γ = ge/2m, where g is
the Zeeman correction term (g-value). Thus, quantum mechanically, each integral
multiple ħ of orbital angular momentum has an associated orbital magnetic moment
of magnitude β = |e|ħ/2m = γħ/g.

We now return specifically to the free electron. The component μz of electron spin
magnetic moment along the direction of the magnetic field B applied along the direction
z is

where ge is the free-electron g-factor. The negative sign arises because of the negative
charge on the electron and the choices of μe and ge as positive quantities.

Magnetic Field Entities & Units

A very important quantity for the molecular spectroscopy course is the magnetic-
dipole moment μe, which has units of J T1. Each magnetic species (magnetic dipole
moment) can change its energy, i.e., its orientation in an external field B, by interacting
with external magnetic excitation. The macroscopic collection of N such magnetic dipoles
in a given volume V has the resultant macroscopic moment per unit volume, called
the magnetization, M,

which has units of J.T1.m3 (the same unit as for H). M is thus the net magnetic
moment per unit volume. Since the magnetic moments of nuclei, atoms and
molecules are proportional to the angular momenta of these species, it is convenient
to write each such proportionality factor as a product of a dimensionless g factor and
a dimensioned factor (a conglomeration of physical constants) called the magneton.
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 Basics of EPR Spectroscopy

e =J

where  has the same units as vector m; g is the magnitude of the electron Zeeman
factor for the species considered, and J is the general angular-momentum vector.
This is taken to be dimensionless (in units of h— , h/2), as its units (J.s) have been
incorporated into ; the factor a (=1) is defined below. The circumflex (^) is
placed above symbols such as J and μ when it is desirable that these be interpreted
as quantum-mechanical operators. Such operators can simultaneously be vectors.
For free electrons, e = 1, J is the electron spin operator S, so that β becomes

where βe is called the Bohr magneton; e is the electronic charge, h— is the Planck‟s
constant and me is the mass of the electron. The Zeeman splitting constant for the
free-electron Zeeman factor
ge = 2.0023193043617(15)
is one of the most accurately known of the physical constants.

While for the magnetic nucleus, J is the nuclear spin angular momentum operator, I,
and e = +1, and therefore,

where mp is the mass of the proton (1H).

We can consider next the magnetic moment m in a magnetic field B, where m may
describe either a nuclear or an electron magnetic dipole. Its component mz along B
(taken along z-direction) is generally defined as

Here U(B) is the potential energy of a magnetic dipole of moment μ in an applied

magnetic field B, and the use of the partial derivative symbols indicates that the only
parameter to be varied is the magnetic field. In most situations, μ may be defined in
terms of its scalar product with B

U=μ•B
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 Basics of EPR Spectroscopy

U = |μB|cos(μ  B)

where (μ  B) represents the angle between μ and B. For a given value of B, there is a
minimum energy |μB|, which occurs when the angle (μ  B) is equal to 0, that is, the
magnetic moment is parallel to the direction of B; the maximum energy +|μB| occurs
when (μ  B) = ; at intermediate angles, the potential energy U falls between these two
extremes.

Magnetic Energies & Energy States

Since the individual-particle magnetic potential energy E is proportional to the magnetic

moment (μ), the quantization of spin angular momentum in a specified direction leads to
the quantization of the energy levels of a magnetic dipole in a magnetic field. If the
direction z is chosen to be along B0, application of the expression E =  μz.B0 to a „spin-
only‟ system and substitution of geβems for μz give a set of energies, Ei = ge.βe.B0.ms .
For a single unpaired electron, the possible values of ms are ms = +½ and ms = ½, hence
the two possible values of μz are ∓ge.βe and the values of E are  ½ ge.βe.B0 .These
energies are known as Zeeman energies. Adjacent energy levels are separated by ΔE =
Eupper  Elower = ge.βe.B0  γe.ħ, corresponding to Δ ms = 1.

Interaction of Magnetic Dipoles with ELECTROMAGNETIC RADIATION

Spectroscopic transitions between the two electron spin Zeeman levels may be induced by
an electromagnetic Field B1 (EMR) of the appropriate frequency  provided the photon
energy h matches the energy separation, ΔE, between the spins energy-levels. Thus ΔE
= h  ge.βe.B0 where B0, the applied magnetic field that satisfies the resonance
condition. The conservation of angular momentum imposes a selection rule of Δms =  1
to such spectroscopic transitions because the photon has one unit (ħ) of angular
momentum. Thus there is a second requirement, other than energy requirement, that
must be met for a magnetic transition to take place.

Let us briefly think in terms of absorption and emission of individual photons by the
unpaired-electron system. The photon has its spin component (+ħ) along or opposed to its
direction of motion. This corresponds to right and left circular polarization of the linearly
polarized light. The photon has no magnetic moment. For absorption, depending on its
direction of approach relative to the axis of the electron spin, it can deliver either energy
h and angular momentum (photon type ) or merely energy (photon type ). To meet
the energy requirement (ΔE), several photons can cooperate, but only photon of type 
can be involved, in order to match the condition of total (photon + electron) angular-
momentum conservation.

The transitions between the Zeeman levels require a change in the orientation of the
electron magnetic moment. Hence transitions can occur only if the electromagnetic
radiation can cause such a reorientation. To make transitions possible, the
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 Basics of EPR Spectroscopy

electromagnetic radiation must be polarized such that the oscillating magnetic field has
a component perpendicular to the static magnetic field. The requirement of a suitable
oscillating perpendicular magnetic field (i.e.,  photons) is easily met at microwave
frequencies. If we apply the electromagnetic radiation polarized such that its oscillating
magnetic field B1 (EMR) is oriented parallel to the static magnetic field B, then the effect
of the radiation would merely cause an oscillation at frequency  in the energies of the
Zeeman levels. Generally no reorientation of the electron magnetic moment would occur.
In this case no spectroscopic transitions are possible.

g-factor calculation for Co2+ impurity in MgO (with the magnetic field value of 162.906
mT  1629.06 G) using the resonance condition equation,

Due to hyperfine splitting, hyperfine splittings associated with real absorptions occur in
multiples. EPR is a high resolution technique based on being able to resolve these
peaks. The peaks are broadened by relaxation processes. These are known as T1 and
T2 processes. T1 processes are observable along the axis of the applied static magnetic
field (longitudinal). T2 processes are observable transverse to this field (transverse). T2
broadening is always observed whereas T1 broadening is usually only significant during
saturation (very high radiation intensity).

Longitudinal (spin-lattice) Transverse (spin-spin)

n exp(-gβHlkT)

Absorption
kN = 1/T1

n 1
No net change in n/ n, but  still decreases.

Figure Thermal populations of FigureDipolar spin flips and

energy levels and spin-spin relaxation
spin-lattice relaxation from the kN2 = 1/T2 = R2
excited energy level.
kN1 = 1/T1 = R1

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 Usually whatever causes T1 relaxation also causes T2 relaxation, so
1/T2 > 1/T1, so T2 < T1, so the linewidth is determined by T2: /2 = 1/T2

Classical theory:
Electron spin moment interacts with B0 E

applied electromagnetic radiation

h

1
ms = —
2
Quantum theory:
Separation of the degenerate spin energy
levels are due to the interaction of the
magnetic moments with the applied
Energy

static magnetic field (B0) and the

spectroscopic transitions between spin
energy levels concomitantly
induced by oscillating B1 magnetic field
1
(electromagnetic radiation!) applied in
ms = -—
2 the perpendicular direction to the
external magnetic field.