Epr

ELECTRON PARAMAGNETIC RESONANCE SPECTROSCOPY (EPR)
LECTURE NOTES: DR. CYRIAC MATHEW

Lecture notes: Dr. Cyriac Mathew
EPR spectroscopy is applicable to species (atoms, molecules or ions) containing one or more electrons with
unpaired spins, and is observed in the microwave region of electromagnetic radiation. Majority of stable molecules
are held together by bonds in which electrons are paired. In such cases there will be no net electron spin and hence
such molecules do not exhibit EPR spectrum. On the other hand, some atoms and molecules contain one or more
electrons with unpaired spins and these substances are said to be paramagnetic and exhibit EPR spectra. Hence the
name Electron Paramagnetic Resonance (EPR) spectroscopy. It is also known as Electron Spin Resonance (ESR)
spectroscopy. Like protons, electrons also possess the property of intrinsic spin angular momentum, S. This
generates a magnetic moment, called spin magnetic moment, . Unlike protons, the spin angular momentum and
spin magnetic moment are in opposite direction; in protons, they are in the same direction. In addition, the electron
has orbital motion and hence possesses orbital angular momentum (L), which also produces magnetic moment.
Generally, in EPR we consider only the spin
angular momentum. When placed in an
S
external magnetic field spin angular
momentum will interact with the external
-spin (1/2)
field. An electron has spin, s = .

Therefore, there will be two orientations
( 2 12 1 2 ) for the spin in an external E

magnetic field, which are designated by,
ms = . In the absence of an external in the absence
-spin (-1/2)
Lectrue notes Dr. Cyriac Mathew
magnetic field these levels are degenerate of external field

(have equal energy). However, when a Energy
in the presence B
magnetic field is applied, the degeneracy
of external field
will be removed. When a paramagnetic of strength B S
species absorbs a quantum of Fig 1 Splitting of the energy levels for an electron in the
Lecture notes : Dr. Cyriac Mathew Lecture notes: Dr. Cyriac Mathew Lecture notes: Dr. Cyriac Mathew
electromagnetic radiation in the presence of external magnetic field.

microwave region, electron is excited from
one spin energy state to the other spin energy state which has higher energy. In the low energy state, the spin
magnetic moment is aligned with the external magnetic field which is represented by, Ms = . In the high-energy
state, the magnetic moment is opposed to the external field and is represented by, Ms = +. The potential energy of
a classical dipole of moment of the electron in a magnetic field of strength B is given by, E B cos (1),
where denotes the angle between the direction of the magnetic moment and the direction of the applied
magnetic field B. The minus sign in the above equation shows that the energy is minimum when the spin angular
momentum is oriented antiparallel to external field. Hence -spin state will be the high energy state and -spin state
will be low energy state.
The magnetic moment generated from an electron spin is related to the spin angular momentum by the

equation, g e S ( S 1) .(2), where g is a dimensionless constant which is usually known as the Lande
splitting factor or simply as the g-factor. It is a physical property of the electron. For free electron g has the value of
e
2.00232. e is the Bohr magneton which is the unit of magnetic moment of the spinning electron. e where
2me
me is the mass of the electron ( e = 9.2741 1021 JT 1). The component of the electron spin magnetic moment along
1
the Z-direction is given by, z g e M s ..(3) . Therefore, from equations (1) and (2) the energy levels of an
electron in an external magnetic field of strength B will be, E g e BM s . (4).
Therefore, the energy level difference between the two states, E 12 g e B ( 12 g e B) g e B . (5)
A transition will occur between these two states, when the energy of the quantum of radiation, , is equal to the
difference in energy, E, between the two spin states of the electron is supplied. The EPR experiment consists of the
measurement of such energy differences. The magnetic field generally employed is about 0.34 T (Tesla).
Assuming g = 2.0 the frequency at which an unpaired electron in a field of 0.34T absorb energy will be,
g e B 2.2 9.274 1024 JT 1 0.34T
9.518 109 9.518GHz
h 6.626 10 Js
34
Thus, the EPR transitions occur in the microwave region of the electromagnetic spectrum. For a typical EPR
experiment the energy difference E corresponds to 103 kJ mol1 or about 1 cm1. The magnetic moment of an
unpaired electron is about 1000 times that of the proton, so that the sensitivity of ESR (or EPR) is very much higher
than NMR. ESR spectra can be recorded for radical concentration down to 10 1 mol dm3 irrespective of the number
of non-radical species present. The field strength commonly used in EPR is 0.34 T and for this field the precessional
frequency of the electron is 9.5 GHz, which is much higher than that of a proton.
EPR transitions are caused by the interaction of the electron spin magnetic moment with the oscillating
magnetic field of the incident microwave radiation. To carry out an EPR experiment, the sample under study is
placed between the poles of an electromagnet and it is irradiated with an appropriate microwave radiation. The
magnetic field is then varied to reach the resonance condition. When the incident microwave frequency matches
with the separation between the electron spin energy levels, the microwave radiation will be absorbed by the
sample and is monitored by means of a detector. EPR spectra are plotted as the intensity of absorption verses the
applied magnetic field.
A magnetic dipole never points exactly along or against the direction of the applied magnetic field. The
interaction between the magnetic moment and the applied filed B generates a torque pulling to align the magnetic
moment towards B. Since the electron is spinning, the effect of the torque is to cause a type of motion called
precession, similar to the rotation of a spinning top tilted from the vertical. This is called Larmor precession. (The
same type of motion occurs when a magnetic nucleus is placed in an external field, which is used in NMR). The
angular velocity of the precessional motion is called Larmor precessional frequency, . It is proportional to the
strength of the applied magnetic field; B. Under the resonance condition, the Larmor frequency of the unpaired
electron will be same as the frequency of the incoming microwave radiation.
The g-factor
Different EPR spectrometers may use different microwave frequencies and magnetic field used also may be
varied depending on the sample to obtain resonance signals. Therefore, the signal position could not be represented
by microwave frequency or magnetic field. Hence it is convenient to refer the observed absorption in terms of its g-
value. This could be explained in the following way.
Molecules of different types come into resonance at different applied magnetic fields. This is because the
application of an external magnetic field may generate an internal magnetic field in the sample by inducing the
electrons to circulate through the molecular framework. This orbital motion give rise to a small additional magnetic
field. The magnitude of the additional field would be proportional to the applied magnetic field itself. The electron
spin magnetic moment interacts with this local magnetic field. In addition, there may be permanent local fields
2
which do not require external magnetic field. These local fields may reinforce or oppose the applied external
magnetic field. Such local fields are accounted for by allowing the g-factor to vary. That is,
E h
g eff . Where Bres is the magnetic field at resonance.
e Bres e Bres
For a free electron in vacuum the g-value is 2.00232. In chemical systems, the unpaired electron occupies an
orbital which may be localized on a single atom or extensively delocalized across the molecule or the radical. The g-
value now reflects the nature of the orbital. The value of g may then be considerably different from 2.0. It seldom
falls much below this value but may reach up to 9.0 or more. The g-factor can thus be considered as a quantity
characteristic of the molecule in which the unpaired electrons are located. The g-value deviations from free electron
value are much like the chemical shifts in NMR. Most free radicals have very low molecular symmetry and hence the
orbital angular momentum will be generally reduced leading to a very small spin-orbit coupling. As a result, the g-
values are nearly equal to the free electron value. The g-value for an unpaired electron in a gaseous atom or ion for
which the Russel-Saunders coupling is applicable is given by,
J ( J 1) S ( S 1) L( L 1)
g 1 , where L is the total orbital angular momentum, S is the total spin angular
2 J ( J 1)
momentum, J is the total angular momentum.
In metal ions, the 'g' values often greatly differ from the free electron value. The magnitude of 'g' also depends
upon the orientation of the molecule containing the unpaired electron with respect to the magnetic field. In solution
or in the gas phase, 'g' is averaged over all orientations because of the free motion of the molecules. If the
paramagnetic radical or ion is located in a perfectly cubic crystal site (Oh or Td site), the 'g' value is independent of
the orientation of the crystal and is said to be isotropic.
In a crystal of lower symmetry, the 'g' value depends upon the orientation of the crystal with respect to the
magnetic field and is said to be anisotropic. The 'z' direction coincides with the highest fold rotation axis, which can
be determined using X -rays. When the z-axis is parallel with the external magnetic field, the 'g' value is called, g ,
also known as gz. The 'g' values along the x-and y-axes are called gx and gy. These are referred to as g. The reason is
that the external magnetic field is perpendicular to the z-axis. In a tetragonal site, gx = gy.
If '' is the angle between the magnetic field and the z-axis, the experimental 'g' value is given by the following
equation for a system with axial symmetry:
There will be inequality in 'g' values even if there are small distortions. These cannot be detected by X-ray diffraction.
However, EPR can detect these small distortions from the inequalities in 'g' values.
Presentation of Spectrum
In general, EPR absorptions are broad compared to NMR absorptions. Therefore, the measurement and
observation of the signals will be difficult. For this reason, EPR spectra are plotted as the first derivative (the slope)
of the absorption curve against the strength of the magnetic field. Much higher sensitivity can be achieved by this
method where absorption is very broad.
3
A number of factors affect the shape, position and width of an EPR signal. The intensity of an EPR
absorption is the total area under the resonance curve and it is proportional to the concentration of the
paramagnetic species present. This relation could be used

for estimating the amount of the paramagnetic substance
by measuring the ratio of the area for a known amount of
the sample to that of the unknown sample. This procedure Broad signal
Absorption A
is valid if the known and unknown samples are of similar
type of spin systems, such as free radicals. A commonly

used standard in EPR is 2,2-diphenyl-1-picrylhydrazyl
(DPPH). It is a dark-colored
crystalline powder composed
of stable free-radical B
molecules. DPPH has two

major applications, one is for
monitoring chemical
DPPH reactions involving radicals,
Derivative signal
and other as a standard for the position and intensity of
electron paramagnetic resonance signals.
FINE AND HYPERFINE SPLITTING B

dA/dB
In EPR spectra two kinds of multiplet structure is
observed. One is the fine structure, which occurs mainly in
crystals containing more than one unpaired electron spin,
and the hyperfine structure, which arises when an unpaired

can get close to a nucleus with non-zero spin. The hyperfine
structure is a smaller effect compared to fine structure.
Nuclear hyperfine splitting:

The simplest case is hydrogen atom, where an unpaired electron interacts with a proton, which has a spin (I)
of . The ESR spectrum of hydrogen shows a pair of lines instead of a single line. The lines are separated by the
hyperfine coupling constant, a = 0.05 T. The electron-nucleus coupling constants are very much larger than those of
nucleus-nucleus interactions. This is because (i) an electron can approach a nucleus more closely than can another
nucleus and (ii) the electrons magnetic dipole is about 1000 times larger than that of the nucleus. Thus, in the
hydrogen atom electron resonance shows two equal lines with a separation of about 0.05 Tesla. This is equivalent to
a frequency of about 1400 MHz. (For 0.34T the
frequency is 9.5 GHz). For most organic molecules 0.0507 T
with an unpaired spin the coupling constants are of
the order of 2 20 MHz. These are smaller than that
of the hydrogen atom because an unpaired electron
in a molecule is never confined to just one nucleus
and seldom even to one bond. But it can move over
several bonds with relative ease, spending only part
of its time at any one nucleus. This may be

understood in another way considering the electron
density. In the hydrogen atom, the electron density of
the unpaired electron could be taken as 1, as the ESR spectrum of hydrogen atom showing hyperfine splitting
electron is in the atom and nowhere else. To a good
4
approximation the magnitude of the coupling constant is directly related to the electron density by the following
equation, a = Q. Here a is the coupling constant, Q is the intrinsic coupling for unit electron density, and is the
electron density. This equation is called McConnel relationship.
The spin of the hydrogen atom, I = . In the presence of strong magnetic field the spin can take (2I + 1)
values, MI = (for hydrogen MI = mI). The energy of the electron now gets modified by the orientation of the
magnetic moment of the nuclear spin, which can also be aligned parallel or antiparallel to the external magnetic
field. The electron spin experiences a slightly different magnetic field depending on whether the nucleus is parallel
Selection rule: MS = 1, MI = 0 Spin orientations

of proton
MI =
Ms =
MI = (P)
Ms =
(P) (Q) (R)
(No external
MI = (Q) (R)
field) a
Ms =
MI = B
A familiar Tree diagram
Bj P, Q and R are transitions
(External field B) B0 Bk
a=0 a = (Bk Bj)

or antiparallel to the applied filed. Each orientation of the electron spin can thus be associated with either of the two
proton spin orientations. Thus, the nuclear hyperfine interaction splits each of the electron Zeeman levels into two
levels as shown in the figure. The probability
that any one of the nuclei will have mI = +
is almost the same as that it will have m I =

. Hence the ESR spectral lines of the
hydrogen atom will be split into two
components of equal intensity. The Hyperfine interaction
a with proton 'a'
hyperfine splitting is independent of the
applied field.
The interaction between the

electron spin and the molecular spin is Hyperfine interaction
expressed by the term aMSMI where a is with proton 'b'
a
the hyperfine splitting constant. Therefore,
the energy level, 1 2 1
E = g eMSB + aMSMI.
Radicals containing a set of equivalent
Protons:
Let us consider a system of electron

spin interacting with two equivalent protons.
A simple way of describing it is to regard that
proton 1 splits the original single line due to EPR spectrum of CH2OH radical at pH 1.0
5
the electron spin transition into a doublet, each line is then further split into two by the interaction with proton 2. A
set of three energy levels with doubly degenerate central energy level results. The CH2OH radical, at low pH, is an
example of such a system. When the pH of the solution is sufficiently low ( 1.0), the OH protons contribute no
detectable hyperfine splitting since it undergoes rapid exchange. The intensity ratio of signals will be 1 : 2 : 1.
Let us now consider a free radical with three equivalent protons. Eg. CH3 . The three protons give rise to
four orientations of spin. As a result the
signal appears as four lines with intensity
ratio, 1 : 3 : 3 : 1.
Equivalent protons produce

hyperfine structure based on (n + 1) rule
similar to that of NMR. Pascals triangle may
be used to measure relative intensities.
Nuclei
EPR spectrum of CH3 radical
0 1
1 1 1
The benzene radical anion C6H6 give rise a seven-line spectrum
2 1 2 1 based on (n + 1) rule. The appearance of seven equally spaced
lines shows that all six hydrogens are equivalent, and therefore
3 1 3 3 1 that the unpaired electron is coupling equally with all six
hydrogens rather than localized at one particular position. Since
4 1 4 6 4 1 12
C is non-magnetic, no further hyperfine splitting is produced.
Pascal's triangle Another example is CH3CHOCH2CH3 radical. The spectrum
shows hyperfine coupling with protons of -CH3, CH, and -CH2.The -CH3 is too far to contribute to splitting. First
the -CH3 couple and splits the signal into four. The CH proton further splits each into doublets. Each of these
signals is split into triplet by the -CH2. Therefore, the spectrum shows altogether 24 lines.
aCH3
aCH
aCH2
CH3-CH-O-CH2-CH3
For naphthalene radical protons on carbon atoms 1, 4, 5 and 8 are equivalent. Similarly, 9 1
10
protons on carbon atoms 2, 3, 6 and 7 are also equivalent. Thus, there are two sets of 2
8
equivalent protons. The first set splits the absorption into five lines and the next set split
each of these in to a further five lines. Hence hyperfine splitting consists of 5 5 = 25 lines. 7 5
3
6 4
6
The Fine structure in EPR spectra
So far, we have considered free radicals which contain only one unpaired electron. However, there are many
systems which have several unpaired electrons, such as transition metal ions. The fine structure of EPR arises due to
electron-electron coupling which generally arise in crystals. When more than one unpaired electrons are present the
system can exist in triplet and higher multiplet levels. A simple example is the dioxygen molecule which exhibit
triplet ground state.
A molecule which contain two unpaired electrons has a total spin, S = 1, ( + ). Hence the multiplicity is
(2S + 1) = 3. The molecule is said to be in the triplet state. A singlet state may also arise if the electrons are in
different orbitals and have opposite spins, S = 0. (If they are in the same spatial orbital total spin will be zero, by Pauli
Principle). When total spin S = 1, it can have three orientations, +1, 0, 1, in an external magnetic field. When there
are two unpaired electrons (or more than one unpaired electrons) there will be interactions between electrons
which is called dipolar interactions. As a result, non-uniform splitting of the triplet state occurs. This happens even in
the absence of external field. The Ms = 0 level become lower in energy and Ms = 1 levels become higher in energy.
Such splitting is called zero-field splitting. The following diagram shows splitting without and with zero-field splitting.
MS
MS = 1 +1
MS = 0, 1 1
MS = 0, 1
MS = D
0 0
E MS = 1 E
1
No external No external B
B
magnetic field External magnetic field magnetic field External magnetic field
(a) Splitting without zero-field splitting (b) Splitting with zero-field splitting D
The zero-field splitting is represented by D. The allowed transitions are Ms = 1. The two transitions shown in the
figure is responsible for the fine structure of the spectrum. (For more details, see Introduction to magnetic
resonance spectroscopy, 2nd edn. D. N Sathyanarayana, p. 97 and Fundamentals of Molecular spectroscopy, C. N.
Banwell and E. M. McCash).
Kramers Degeneracy
The EPR spectra of transition metal complexes are markedly different from the spectra of small organic and
inorganic free radicals in solution. In transition metal complexes, the energy levels available for the unpaired
electrons may be split by the intrinsic field of the surrounding ligands. The type and extend of splitting depends upon
the nature of the ligands and their arrangement around the metal ion.
When a system contains an odd number of unpaired electrons, the spin degeneracy of every level remains at
least doubly degenerate, in the absence of an external magnetic field. This is known as Kramers degeneracy
theorem. For an even number of unpaired electrons, the spin degeneracy may be lifted entirely by the crystal field
and this phenomenon is known as zero-field splitting which has been discussed earlier for systems containing two
unpaired electron spins. Therefore, metal ions with odd number of d-electrons always has as its lowest level at least
a doublet, which is called Kramers doublet.
7
McConnell Relationship
The hyperfine structure of an EPR spectrum is a kind of fingerprint that helps to identify the radicals present
in a sample. Because the magnitude of the splitting depends on the distribution of the unpaired electron near the
magnetic nuclei present, the spectrum can be used to map the molecular orbital occupied by the unpaired electron.
In C6H6 the hyperfine splitting is 0.375 mT (milli Tesla) or 1420 MHz. One proton is attached to each carbon atom
whose unpaired electron spin density is 1/6th, because the electron is spread uniformly around the ring. Therefore,
the hyperfine splitting caused by a proton when the electron is entirely confined on a particular carbon atom
adjacent to that proton will be 6 0.375 = 2.25 mT. If in another aromatic radical we find a hyperfine splitting
constant a, then the spin density (the probability that an unpaired electron is on the atom) can be calculated using
the McConnell equation: a = Q. Q is taken as 2.25 mT. Here a is the hyperfine splitting constant of the unpaired
electron to a proton and is the spin density (unpaired electron density) at the carbon to which the proton is
attached.
0.375
The hyperfine structure of the EPR spectrum of the radical anion (naphthalene) can be interpreted as
arising from two groups of four equivalent protons. Those at 1, 4, 5 and 8 positions in the ring have a = 0.490 mT and
for those in 2, 3, 6 and 7 positions have a = 0.183. the corresponding spin densities obtained using McConnell
relation are; 0.490/2.25 = 0. 22 and 0. 183/2.25 = 0.08 respectively.
0.22
0.08
Q. Spin density of (anthracene) is shown below. Predict the form of its EPR spectrum.
0.097 0.193
10 1 2
0.048 9 3
8 4
7 6 5
The three different spin density values show that there are three different sets of protons. The hyperfine splitting
constant for protons with spin density 0.193 is; 0.193 2.25 = 0.43 mT; that of 0.097 is 0.097 2.25 = 0.22 mT and
that of 0.048 is 0.048 2.25 = 0.11 mT. Protons on carbon 1 and 6 split the signal into 1:2:1 triplet with splitting
constant 0.43 mT. Each of these is split into quintets by protons on carbon atoms 2, 5, 7 and 10, with intensity
1:4:6:4:1 and splitting constant 0.22 with a total of 15 lines. Each of these is further split into a quintet by protons 3,
4, 8 and 9 with intensity 1:4:6:4:1 and splitting constant 0.11 mT. Thus, the total number of lines will be 15 5 = 75.
References:
1. Introduction to Magnetic Resonance Spectroscopy ESR, NMR, NQR, 2nd edn. D. N. Sathyanarayana
2. Physical Methods in Chemistry, Russel s Drago
3. Fundamental of Molecular spectroscopy, C. N. Banwell
4. An introduction to spectroscopic Methods, Vol. II, F. Sheinmann
5. Organic Spectroscopy, William Kemp

6. Molecular Spectroscopy, G Aruldhas
7. Physical chemistry, P. W. Atkins
8. Fundamentals of Molecular Spectroscopy, P. S. Sindhu

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ELECTRON PARAMAGNETIC RESONANCE SPECTROSCOPY (EPR)

LECTURE NOTES: DR. CYRIAC MATHEW

field. An electron has spin, s = .

( 2 12 1 2 ) for the spin in an external E

magnetic field these levels are degenerate of external field

electromagnetic radiation in the presence of external magnetic field.

momentum, J is the total angular momentum.

method where absorption is very broad.

paramagnetic species present. This relation could be used

type of spin systems, such as free radicals. A commonly

molecules. DPPH has two

electron paramagnetic resonance signals.

FINE AND HYPERFINE SPLITTING B

and the hyperfine structure, which arises when an unpaired

Nuclear hyperfine splitting:

of its time at any one nucleus. This may be

electron density. This equation is called McConnel relationship.

Selection rule: MS = 1, MI = 0 Spin orientations

a=0 a = (Bk Bj)

is almost the same as that it will have m I =

The interaction between the

Let us consider a system of electron

Equivalent protons produce

be used to measure relative intensities.

5. Organic Spectroscopy, William Kemp

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