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Epr

Epr

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03/24/2014

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1
Chapter 2E.P.R.SPECTROSCOPY
This spectroscopy is applicable to paramagneticcomplexes and is observed in the microwave region of electromagnetic radiation.When a paramagnetic molecule absorbs a quantum of electromagnetic radiation in the microwave region,electron is excited from one spin energy state to anotherspin energy state, which has higher energy.An electron has a spin, s =
½. The spin
 – 
angularmomenta, m
s
 
 
½, have equal ener 
gy in the absence of magnetic field. However, when a magnetic field isapplied, the degeneracy is resolved, that is, removed. Inthe low energy state, the spin magnetic moment isaligned with the external magnetic field and hence, m
s
=-
½. In the high
-energy state, the magnetic moment isopposed to the external field and hence, m
s
= +
½.
 A transition will occur between these two states,when the energy of the quantum of radiation,
, is equalto the difference in energy,
E, between the two spinstates of the electron. That is,
E = h
= g
H
0
,where,
h
is the Planck 
s constant,
is the frequency
of radiation,
is the Bohr magneton,
H
0
is the
external magnetic field strength and
g
is the
spectroscopic splitting factor.
Characteristics of 
g
 
1.
 
It is not a constant.
 
22.
 
It is a tensor quantity. That is, it depends on threeparameters, namely, magnitude, direction andarbitrary number of indices.3.
 
For a free electron, g = 2.00234.
 
In metal ions, the
g
values often greatly differ 
from the free electron value.5.
 
The magnitude of 
g
depends up on the
orientation of the molecule containing theunpaired electron with respect to the magneticfield.6.
 
In solution or in the gas phase,
g
is averaged
over all orientations because of the free motion of the molecules.7.
 
If the paramagnetic radical or ion is located in aperfectly cubic crystal site (O
h
or T
d
site), the
g
 
value is independent of the orientation of thecrystal and is said to be isotropic.8.
 
In a crystal of lower symmetry, the
g
value
 depends up on the orientation of the crystal withrespect to the magnetic field and is said to beanisotropic.9.
 
The
z
direction coincides with the highest fold
rotation axis, which can be determined by X
 – 
 ray. When the z-axis is parallel with the externalmagnetic field, the
G
value is called, g
||
, and itis also known as g
z
. The
g
values along the x
-and y-axes are called g
x
and g
y
. These arereferred to as g
. The reason is that the externalmagnetic field is perpendicular to the z-axis.10.
 
In a tetragonal site, g
x
= g
y
.11.
 
If 
is the angle between the magnetic field and
the z-axis, the experimental
g
value is given by
 
3the following equation for a system with axialsymmetry:g
2
= g
||2
cos
2
+ g
2
sin
2
 12. There will be inequality in
g
values even if 
there are small distortions. These cannot bedetected by X-ray. However, e.p.r can detectthese small distortions from the inequalities in
g
values.
Types of e.p.r. Instruments
There are two types of e.p.r. Spectrometers:1.
 
X
 – 
band spectrometer2.
 
Q
 – 
band spectrometer
 X 
 – 
band spectrometer 
A frequency around 9400 megacycles per secondand a magnetic field strength around 3000 gauss areemployed. The magnetic field strength can be varied inthe range 1
 – 
10,000 gauss.
Q
 – 
band spectrometer 
 A frequency around 35,000 megacycles persecond and a magnetic field strength around 12,500gauss are used.
Presentation of the Spectrum
The spectrum can be presented in two ways:1.
 
Normal mode.2.
 
Derivative mode.
 Normal mode
 

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