Electron Spin Resonance

Spectroscopy

or
Its fun to flip electrons!

Electron Paramagnetic Resonance spectroscopy

Electron Spin Resonance spectroscopy

Method for studying materials with unpaired electrons. The basic concepts
of EPR are analogous to those of nuclear magnetic resonance (NMR), but
it is electron spins that are excited instead of the spins of atomic nuclei.
EPR spectroscopy is particularly useful for studying metal complexes or
organic radicals.

Diamagnetism
1. Any time two electrons share the same orbital, their spin quantum numbers
have to be different. In other words, one of the electrons has to be "spin-up,"
with , while the other electron is "spin-down," with . This is important when it
comes to determining the total spin in an electron orbital. In order to decide
whether electron spins cancel, add their spin quantum numbers together.
Whenever two electrons are paired together in an orbital, or their total spin is
0, they are called diamagnetic electrons.

2. Think of spins as clockwise and counterclockwise. If one spin is

clockwise and the other is counterclockwise, then the two spin directions
balance each other out and there is no leftover rotation. Note what all of
this means in terms of electrons sharing an orbital: Since electrons in the
same orbital always have opposite values for their spin quantum
numbers (ms), they will always end up canceling each other out. In other
words, there is no leftover spin in an orbital that contains two electrons.

3. Electron spin is very important in determining the magnetic properties of

an atom. If all of the electrons in an atom are paired up and share their
orbital with another electron, then the total spin in each orbital is zero and
the atom is diamagnetic. Diamagnetic atoms are not attracted to a
magnetic field, but rather are slightly repelled.

Paramagnetism
1. Electrons that are alone in an orbital are called paramagnetic electrons.
Remember that if an electron is alone in an orbital, the orbital has a net spin,
because the spin of the lone electron does not get canceled out. If even one
orbital has a net spin, the entire atom will have a net spin. Therefore, an
atom is considered to be paramagnetic when it contains at least one
paramagnetic electron. In other words, an atom could have 10 paired
(diamagnetic) electrons, but as long as it also has one unpaired
(paramagnetic) electron, it is still considered a paramagnetic atom.
2. paramagnetic atoms are slightly attracted to a magnetic field.
Paramagnetic properties are due to the realignment of the electron paths
caused by the external magnetic field. Paramagnets do not retain any
magnetization in the absence of an externally applied magnetic field,
because thermal motion randomizes the spin orientations. Stronger
magnetic effects are typically only observed when d- or f-electrons are
involved.

Principles of EMR spectroscopy

Classical theory:
Electron spin moment interacts with
applied electromagnetic radiation

B0

Quantum theory:

1
ms =
2

Resonance condition
h = gBB0

Energy

transitions between energy levels

induced by magnetic field

ms =
2

The EPR experiment

Put sample into
experimental
magnetic field (B)
Irradiate
(microwave
frequencies)
Measure
absorbance of
radiation as f(B)

Weil, Bolton, and Wertz, 1994, Electron Paramagnetic Resonance

The hyperfine effect

The magnetic field experienced by the unpaired electron
is affected by nearby nuclei with non-zero nuclear spin

Weil, Bolton, and Wertz, 1994, Electron Paramagnetic Resonance, New York: Wiley Interscience.

Hyperfine splitting of EPR spectra

The magnitude of the splitting and the
number of lines depend upon:
The nuclear gyromagnetic ratio
The magnitude of the interaction between the
electronic spin and the nuclear spin
Magnitude of the splitting typically decreases
greatly with increasing numbers of bonds between
the nucleus and unpaired electron

Some nuclei with spins

Element

Isotope

Nuclear
spin

No of
lines

%
abundance

Hydrogen

99.985

Nitrogen

14

99.63

15

0.37

Vanadium

51

7/2

99.76

Manganese

55

Mn

5/2

100

Iron

57

Fe

2.19

Cobalt

59

Co

7/2

100

Nickel

61

Ni

3/2

1.134

Copper

63

Cu

3/2

69.1

65

Cu

3/2

30.9

95

Mo

5/2

15.7

97

Mo

5/2

9.46

Molybdenum

Diagram of an ESR spectrometer

Circulator
Detector

Klystron
Microwave source

Cavity
N

cryostat

Spectrophotometer
Detector
Light source