Electron Spin Resonance

Spectroscopy
 ESR
– ESR is a branch of study in which
electromagnetic radiation (usually
microwave frequency) is absorbed by
molecules, ions, or atoms possessing
electrons with unpaired spins.
– In both ESR and NMR, the sample material is
immersed in a strong magnetic field and
exposed to an orthogonal low amplitude high
frequency field.
• ESR requires microwave frequency, while
NMR requires lower radio frequency
 ESR Spectroscopy
• Electron Spin Resonance Spectroscopy
• Also called EPR Spectroscopy
– Electron Paramagnetic Resonance Spectroscopy
• Non-destructive technique

• Applications
– Extensively used in transition metal complexes
a)Deviated geometries in crystals, Density of ions, number
of ions in the sample.
b)Position of insertion, symmetry of the lattice position.
c) Couplings, line widths, dynamics and lattice vibrations
 What compounds can you
analyze?
• Applicable for species with one or more unpaired
electrons
– Free radicals
– Transition metal compounds, metal halides,
nitrides, oxides, phosphides.
• Useful for unstable paramagnetic compounds
generated in situ
– Electrochemical oxidation or reduction
 Energy of Transitions
• ESR measures the transition between the
electron spin energy levels
– Transition induced by the appropriate
frequency radiation
• Required frequency of radiation dependent
upon strength of magnetic field
– Common field strength 0.34 and 1.24 T
– 9.5 and 35 GHz
– Microwave region
• The absorption of energy causes a transition
of an electron from a lower energy state to a
higher energy state.

• In EPR spectroscopy the radiation used is in

the gigahertz range.

• Unlike most traditional spectroscopy

techniques, in EPR spectroscopy the
frequency of the radiation is held constant
while the magnetic field is varied in order to
obtain an absorption spectrum.
 How does the
spectrometer work?
• The radiation source usually used is called a
klystron

• They are high power microwave sources

which have low-noise characteristics and
thus give high sensitivity

• A majority of EPR spectrometers operate at

approximately 9.5 GHz, which corresponds to
about 32 mm ( Q-band)

• The radiation may be incident on the sample

continuously or pulsed
• The sample is placed in a resonant cavity
which admits microwaves through an iris.
(An iris is a hole between the waveguide and
cavity in which the size of the opening is adjusted
by a screw.)

• The cavity is located in the middle of an

electromagnet and helps to amplify the
weak signals from the sample.

• Numerous types of solid-state diodes are

sensitive to microwave energy

• Absorption lines are detected when the

separation of the energy levels is equal to
the energy of the incident microwave.
• In practice, most of the external
components, such as the source and
detector, are contained within a microwave
bridge control.

• Additionally, other components, such as an

attenuator, field modulator, and amplifier,
are also included to enhance the
performance of the instrument.
 What causes the energy
levels?

Resulting energy levels of an electron in a

magnetic field
• When an electron is placed within an applied
magnetic field, Bo, the two possible spin states of
the electron have different energies (Zeeman
effect)

• The lower energy state occurs when the

magnetic moment of the electron is aligned with
the magnetic field.

• The two states are labeled by the projection of

the electron spin, MS, on the direction of the
magnetic field, where MS = -1/2 is parallel and MS
= +1/2 is anti parallel state
 Describing the energy
levels
• Based upon the spin of an electron and its
associated magnetic moment
• For a molecule with one unpaired electron
– In the presence of a magnetic field, the
two electron spin energy levels are
E = gmBB0MS
g = proportionality factor mB = Bohr magneton
MS = electron spin B0 = Magnetic field
quantum number
(+½ or -½)
 How ESR is different?
• According to uncertainty principle

∆ E . ∆ t ≈ h/4∏

Since ∆ E = h ∆ν

∆ν = h/4∏ . ∆ t

• So when the life time of electron in the

excited state decreases the lines broaden
• Due to many reasons the absorption lines are very
broad.
• To get finer information ∂A/∂H is plotted against H
to get the first derivative curve. When phase-
sensitive detection is used, the signal is the first
derivative of the absorption intensity
 Spin-Lattice relaxation (T1)
• Excess energy given to either the lattice or the
tumbling solvent molecules.

• Depends on temperature.

• If temperature increases then all these motions

increase leading to effective relaxation

• To minimize this effect esr spectrum is always

recorded at LNT 77 K when thermal energy is
minimum
 Spin – Spin relaxation (T2)
• Excess energy given to neighbouring
electron.

• Independent of temperature

• Has two components

Dipolar interaction

Direct interaction
 Dipolar interaction
• Spinning e- produces a magnetic field which
affects the neighbouring e-

• Since esr spectra are taken in frozen state

spins are locked and this effect becomes
important.

• This leads to low T2 values and hence very

broad lines.
• The interaction includes a 1/r3 term. Where
r is the distance between two neighbouring
electrons.

• If the concentration of unpaired e-

increases then r value decreases leading to
low T2 and hence broad lines. This is called
concentration broadening
• The r value is increased by diluting the
sample with isomorphous diamagnetic
materials
 Direct interaction of e-
• In dipolar interaction e-s interact through
the magnetic fields.

• If concentration of unpaired e- is high then

the spin of e-s can directly interact leading
to line broadening.

• If the hyperfine splitting is of the same

order then only a single broad line is
observed. This is called concentration
narrowing
• Same electron undergoes resonance at
different fields with different operating
frequencies.

• So mentioning the field of resonance may be

misleading.

• g is used to mention the position of the line

E = mBB0MS

g = h ∆ν / mBB0MS
 Proportionality Factor
• Measured from the center
of the signal
• For a free electron
– 2.00232
• For organic radicals
– Typically close to free-
electron value
– 1.99-2.01
• For transition metal compounds
– Large variations due to spin-orbit
coupling and zero-field splitting
– 1.4-3.0
 POSITION OF THE SIGNAL
• Already mentioned g value gives the
position of the signal.

• Actually g is not a constant. It is a tensor

quantity- changes with environment.

• Many systems show g values close to that of

free e-, but deviations are also common.

• Deviations in the order±0.05 may be the

mixing of low lying e.s with the g.s
• g values for the d metal ions (3d)
ranges from 0.2 – 8.
• The wide range is attributed to many
reasons.
 L-S coupling
 Crystal field Splitting
 Presence of inherent magnetic field in the
crystal.
 But L-S coupling and oxidation state of the metal
ion make the g value characteristic
 Reference used
• When the operating
frequency of the
instrument is not known
precisely then DPPH radical
is used as standard.
• It gives five extremely
sharp peaks with intensity
ratio 1:2:3:2:1 (in solid
state one sharp line)
• g= 2.0036[1-∆H/H]
• ∆H – diff between std and
sample
• H – sample field
Proportionality Factor
MoO(SCN)52- 1.935

VO(acac)2 1.968

e- 2.0023

CH3 2.0026
C14H10 (anthracene)
2.0028
cation
C14H10 (anthracene)
2.0029
anion
Cu(acac)2 2.13
 Hyperfine Interactions
• EPR signal is ‘split’ by neighboring nuclei
– Called hyperfine interactions

• Can be used to provide information

– Number and identity of nuclei
– Distance from unpaired electron

• Interactions with neighboring nuclei

E = gmBB0MS + aMsmI
a = hyperfine coupling constant
mI = nuclear spin quantum number
 Hyperfine Interactions

Interaction with a single nucleus of spin ½

 mI

- (1 /2 )
m S = + 1 /2 N
+ (1 /2 )

2
e F IE L D B Z
ZE R O F IE LD 1
- (1 /2 )

m S = -1 /2 N
+ (1 /2 )
 Which nuclei will interact?
• Measured as the distance
between the centers of
two signals
• Selection rules same as
for NMR
• Every isotope has a
ground state nuclear spin
quantum number, I
– has value of n/2, n is
an integer
• Isotopes with even atomic number and even
mass number have I = 0, and have no EPR
spectra
– 12C, 28Si, 56Fe, …

• Isotopes with odd atomic number and even

mass number have n even
– 2H, 10B, 14N, …

• Isotopes with odd mass number have n odd

– 1H, 13C, 19F, 55Mn, …
 Hyperfine Interactions
• Coupling patterns same as in NMR
• More common to see coupling to nuclei with
spins greater than ½
• The number of lines:
2NI + 1
N = number of equivalent nuclei
I = spin
• Only determines the number of lines--not
the intensities
 Hyperfine Interactions
• Relative intensities determined by the
number of interacting nuclei

• If only one nucleus interacting

– All lines have equal intensity

• If multiple nuclei interacting

– Distributions derived based upon spin
– For spin ½ (most common), intensities
follow binomial distribution
 Relative Intensities for I = ½
N Relative Intensities
0 1
1 1:1
2 1:2:1
3 1:3:3:1
4 1:4:6:4:1
5 1 : 5 : 10 : 10 : 5 : 1
6 1 : 6 : 15 : 20 : 15 : 6 : 1
Relative Intensities for I = ½
Relative Intensities for I = 1
N Relative Intensities

0 1

1 1:1:1

2 1:2:3:2:1

3 1:3:6:7:6:3:1

4 1 : 4 : 10 : 16 : 19 : 16 : 10 : 4 : 1

5 1 : 5 : 15 : 20 : 45 : 51 : 45 : 20 : 15 : 5 : 1

6 1 : 6 : 21 : 40 : 80 : 116 : 141 : 116 : 80 : 40 : 21 : 6 : 1

Relative Intensities for I = 1
 Hyperfine Interactions
• Example:
– VO(acac)2
– Interaction with vanadium nucleus

– For vanadium, I = 7/2

– So,
2NI + 1 = 2(1)(7/2) + 1 = 8

– You would expect to see 8 lines of equal

intensity
 Hyperfine Interactions

EPR spectrum of vanadyl acetylacetonate

 Hyperfine Interactions
• Example:
– Radical anion of benzene [C6H6]-
– Electron is delocalized over all six carbon
atoms
• Exhibits coupling to six equivalent
hydrogen atoms
– So,
2NI + 1 = 2(6)(1/2) + 1 = 7
– So spectrum should be seven lines with
relative intensities 1:6:15:20:15:6:1
 Hyperfine Interactions

EPR spectrum of benzene radical anion

 Hyperfine Interactions
• Coupling to several sets of nuclei
– First couple to the nearest set of nuclei
• Largest a value
– Split each of those lines by the coupling
to the next closest nuclei
• Next largest a value
– Continue 2-3 bonds away from location
of unpaired electron
 Hyperfine Interactions
Pyrazine anion
Electron delocalized over ring
Exhibits coupling to two equivalent N
(I = 1)
2NI + 1 = 2(2)(1) + 1 = 5
Then couples to four equivalent
H (I = ½)
2NI + 1 = 2(4)(1/2) + 1 = 5
So spectrum should be a quintet with
intensities 1:2:3:2:1 and each of
those lines should be split into
quintets with intensities 1:4:6:4:1
 Hyperfine Interactions

EPR spectrum of pyrazine radical anion

Hyperfine splitting and anisotropy
• In solution the molecules are under
continuous motion so interactions in
all directions are same
• So hyperfine interaction is said to be
isotropic.
• In the case of solid state depending
upon the orientation of the crystal
field experienced will change
indifferent direction so A is
anisotropic.
• Usually field is considered to be
applied along Z axis. So A along Z axis
is called A||
• A values along X and Y directions
called A|

•A ave = 1/3[A|| + A|]

 Anisotropic systems
• Anisotropy is shown by solids, frozen
solutions, radicals prepared by irradiation of
crystalline materials, radical trapped in host
matrices, paramagnetic point defect in
single crystals.
• For systems with spherical or cubic
symmetry g is isotropic
• For systems with lower symmetry,
g ==> g‖ and g┴ ==> gxx, gyy, gzz

• ESR absorption line shapes show distinctive

envelope
system with an axis of symmetry no symmetry
• Spin Hamiltonian of an unpaired e- if it is present in a cubic field
is

H = g β | Hx.Sx + Hy.Sy + Hz.Sz|

• If the system lacks a spherical symmetry and possess at least

one axis ( Distorted Oh,SP or symmetric tops) then

H = β |gxx Hx.Sx +gyy Hy.Sy + gzz Hz.Sz|

• Usually symmetry axis coincides with the Z axis and H is applied

along Z axis then
gxx = gyy = gL ; gzz = g||
• When the symmetry axis coincides with Z
axis determination of g is simple.

• The crystal is mounted on a sample cavity

and rotated across the field

• The g value varies between gL and g||

Fine structure of esr spectra
• Zero Field Splitting
• Kramer’s theorem
• Effective spin state
• Break down of selection rule
 ESR spectra of metal complexes
• Factors affecting g value
 Operating frequency
 Concentration of unpaired e-
 Ground term of the ion
 Direction of measurement
 Symmetry of the field
 Inherent magnetic field
 Sustaining effect
 Crystal field splitting
 Jahn – Teller distortion
 Zero field splitting
 Mixing of gs and es
Specific examples