Electron Spin Resonance

Spectroscopy

or
Its fun to flip electrons!

Electron Paramagnetic Resonance spectroscopy

Electron Spin Resonance spectroscopy

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 spin of the interacting nucleus
# of lines = 2n(I + ) so I = gives 2 lines, etc.

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

No hyperfine

Hyperfine coupling

1H)

14N)

2 identical I=1/2 nuclei

1 I=5/2 nucleus17
( O)

10 Gauss

If the electron is surrounded by n spinactive nuclei with a spin quantum

number of I, then a (2nI+1) line pattern
will be observed in a similar way to
NMR.
In the case of the hydrogen atom (I= ),
this would be 2(1)() + 1 = 2 lines.

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

Hyperfine splittings multiply with

the number of nuclear spins

Benzoquinone anion radical:

1 proton splits into 2 lines 1:1

2 protons split into 3 lines 1:2:1
3 protons split into 4 lines 1:3:3:1
4 protons split into 5 lines 1:4:6:4:1

At higher temperature:
faster motion - sharper lines
shorter lifetime - smaller signal

H
-

-60 C

20 C

Prushan Example

S
Cu

N
O
F

N
B

O
F

[Cu(Thyclops)]+

77 K Cryogenic ESR Spectrum of [Cu(Thyclops)]ClO 4 in MeOH

Prushan,M.J.;Addison,A.W.;Butcher,R.J.;Thompson,L.K.Copper(II)Complex Tetradentate Thioether-Oxime Ligands Inorganica Chimica
Acta, 358, 3449-3456 (2005).

2nI+1
2x2x1+1

Diagram of an ESR spectrometer

Circulator
Detector

Klystron
Microwave source

Cavity
N

cryostat

Spectrophotometer
Detector
Light source

Hyperfine Splitting
If the odd, unpaired electron is associated with a nucleus with nuclear
spin, can get coupling between the two spins and observe 2I+1 (I =
nuclear spin) peaks or valleys.
Examples:
di-t-butyl nitroxide radical; I(N) = 1;

Hyperfine Splitting
vanadyl [V=O]2+ complex; I (V) = 7/2; 2(7/2) + 1 = 8 peaks

Signal Intensities
Follow Pascal's triangle

superhyperfine splitting
carbon compound; I(C) = 0; 2(0) + 1 = 1 peak. But:
If the odd, unpaired electron spends time around multiple sets of equivalent
nuclei, additional splitting is observed: 2nI + 1; this is called superhyperfine
splitting.
Examples:

Triplet

Quartet

Pentet

Superhyperfine Splitting
Septet

Examples:

Sextet
Superhyperfine splitting is direct
evidence for COVALENCY!

Octet

It is possible for the unpaired electron to spend differing amounts of time on

different nuclei.
The greater the covalency, the greater is the hyperfine splitting.

Triplet: hyperfine splitting.

Doublet: superhyperfine splitting.
Interpretation: electron is spending most of
its time on CH2 protons, but spending
some time on OH.

Pentet: hyperfine splitting.

Pentet: superhyperfine splitting.
Interpretation: electron is spending
most of its time on one set of protons,
but spending some time on other set.

Septet: hyperfine splitting.

IF= , so 2(6)(1/2) + 1 =7
Triplet: superhyperfine splitting.IN= 1, so
2(1)(1) + 1 = 3
So, spending most time on Fs, less on N.

Nonet: hyperfine splitting.

IN= 1, so 2(4)(1) + 1 =9
Pentet: superhyperfine splitting.
IH= 1/2, so 2(4)(1/2) + 1 = 5
So, spending most time on Ns, less on H.

overlapping pentet
of pentets.

Superhyperfine coupling

High-field high-frequency EPR

Microwave frequency

X-band
0.33

Q-band

W-band

1.25

3.5

D-band
4.9

Tesla

Bo
Superhyperfine interactions become more pronounced!

Anisotropic Interactions: The g-tensor

The free electron has a g-value of ge=2.0023
There may be spin-orbit coupling which will effect the ge
lets look at the simple case of Boron, 2p1.
If all the orbitals have same energy then the spin orbit coupling energy
averages to zero over the x,y, and z coordinate.
However, if the atom is placed in a crystal which removes the degeneracy then
the spin orbit coupling becomes asymmetric, px = py but do not equal to pz
Now the observed g-value will depend
upon orientation of the crystal in the
magnetic field.

Axial symmetry
g|| = gz and g = gx = gy
The g value tells you how strong the electron magnetic tensor is in a given
direction.
Therefore if you orientate the crystal in a different direction the energy to
resonate changes and thus the absorption will shift.
The spin-orbit coupling gives a g < g || = ge
This effect is similar to shielding in the NMR experiment.
z
g ||
gz
Bo
gx
B B BB

h g|| H ||
g||

h
H ||

B B BB

Bo
B B BB
B B BB

gy

What happens if the crystal is ground into a

powder?
All orientations are present however there are more
chances that the g will be aligned with the field than g ||.

g
g ||

h
H

ESR spectra of [Cu(MeTtoxBF2)]BF4 in

1:10 BuOHDMF.
(a) Room temperature (295 K) fluid
spectrum (9.464 GHz). (b) 77 K cryogenic
glass spectrum (9.147 GHz).
Prushan, M. J.; Addison, A. W.*; Butcher, R. J.; "Pentadentate
Thioether Oxime Macrocyclic and Quasi-Macrocyclic Complexes of
Copper(II) and Nickel(II)" Inorganica Chimica Acta, 300-302, 992-1003
(2000).