ESR

Interpretation of Lande’s splitting factor (g),

Anisotropy in g factor and hyperfine coupling
constant (A)

V. Shashikala,
Assistant Professor
Department of Chemistry, UCW

24-04-2020, Friday
Splitting of energy levels in an ESR spectrum is given below.

Energy difference between two levels is

ΔE = h = gH ΔE = h = gH

ΔE – energy of transition
h – Planck’s constant
 - frequency
 - 0.9723 x 10-20 erg/gauss, Bohr’s
magneton (it is a factor for converting angular
Figure 1: Energy levels for an electron momentum to magnetic moment)
spin for Ms = + ½ in an applied H – external magnetic field
magnetic field g – Proportionality factor, Spectroscopic
splitting factor or Lande’s splitting factor. (is
also known as Zeeman Splitting factor .
Introduced by German physicist
A. Lande in 1921
g – Proportionality factor (or) Spectroscopic splitting
factor (or) Lande’s splitting factor
 The g (Lande’s Splitting factor) is similar with the 
(chemical shift) in NMR.
It gives the information about the esr signal position
It is a function of the electron’s environment
 It is a dimensionless tensor quantity, it has no units
 For free electron its value is – 2.002319
 For free radicals and some ionic crystals g value is almost
similar with free electron
 In some ionic crystals and transition metal comples g value
varies from 0.2 to 8.
g factor is the actual resonance position of the ESR absorption line

Figure 2: g value in absorbance

peak and first derivative of esr.

Figure 3: EPR spectra of some proteins

and the g values of the peaks
The quantum mechanical calculation of g factor is,

 For purely orbital moments S = 0, J = 1 and

 For purely spin moments L=0 and J = 2
 g value is not a constant but it is a tensor
 The g value for a free electron calculated by using the
above equation is 2 but the actual value of the free electron
is 2.002319. This is due to relativistic correction.

Experimental determination of g factor:

It is determined by measuring the field separation between the centre
of the unknown spectrum and that of a reference substance (DPPH)
whose g value is accurately known.
g = gs [1-ΔH/H]
Hyperfine Coupling constant (A or a):

 Is related to the distance between peaks in an esr spectrum.

 Its magnitude indicates the extent of delocalization of the
unpaired electron over the molecule. It is independent of
applied magnetic field.
 A in epr is analogous to J in NMR.
 This constant may also be calculated.
 The total energy related to electron transitions in EPR is can
be obtained by the following equation.
E = mSgH + A mSmI
The first term is correspond to energy of electron in Zeeman
splitting.
And the second term is due to hyperfine coupling between the
electron and the nucleus.
A is called as the hyperfine coupling constant.
 Hyperfine coupling constant (A or a):

Figure 4: Hyperfine splitting between two

equivalent protons
Figure 5: Hyperfine splitting between two
unequivalent protons
Anisotropy in g factor:
g values of molecules containing unpaired electron depends
upon orientation of molecules with respect to applied magnetic
field.
i. Molecules in solutions and gas phase are free to move in all
directions, thus the g value is expressed as g – averaged.

ii. And in solid state the molecules are not free to move in all
directions the momentum of molecule is restricted.
iii. If the paramagnetic complex or ions are in perfect cubic crystal
field i.e. Oh and Td geometry the g value is represented as
gx = gy = gz
In such cases the g value is equal in all x, y,z directions and is
known as isotropic.
iv. In molecules with axially symmetric like tetragonal and rhombic
systems g value is represented as
Tetragonal – gx = gy  gz
Orthorhombic – gx  gy  gz
 In such cases the g value is known as g - anisotropic

Figure 6: Ellipsoidal representation of Figure 7: gll and g axes in a crystallite with

variations in the g – tensor value in the three or higher fold
x, y and z coordinates
z axis is parallel with the external magnetic field – gll
x and y are perpendicular with the external magnetic field – g
Thus g average is - gavg = 1/3 (gll + g)
g value for any orientation is given by
 is the angle that the principal axis (i.e. gll) makes with the applied magnetic
field.
 Orthorhombic – gx  gy  gz Tetragonal – gx = gy  gz

Figure 8: An idealized absorption and derivative spectrum of axial symmetric

molecules (A) Orthorhombic and (B) Tetragonal system with S = ½
Anisotropy in constant A
Electron nuclei interactions will have several interactions. Among all
Fermi contact interactions and dipole-dipole interactions are predominant

Figure 9: Electron nuclei

interactions resulting hyperfine
interaction

 Fermi contact interaction is predominant in isotropic interactions, i.e.

sample orientation to the external magnetic field does not affect the interaction.
(sample in gas phase and solution phase always exhibit isotropic interactions)
 Dipole-dipole interactions are predominant with anisotropic interactions i.e.
sample orientation does change the interaction. (if the sample is rigid or taken
in solid matrix will have the anisotropic interaction)
Hyperfine anisotropic interaction:
It will have the All and A. To get the average a value the following
equation need to be used
Aavg = 1/3 (All + 2A)

Thank you
Zero field splitting and Kramer’s degeneracy
Quadrupole Interactions

01-05-2020
Friday
Zero field splitting

When a metal ion with more than one unpaired electrons

incorporated in the ligand field, the degeneracy of all the spin
states is lifted even in the absence of external magnetic field.
This splitting is known as the zero field splitting. The
mechanism of zero field splitting is similar to that of second
order spin orbit coupling.
Ms
Ms In an external magnetic field two transitions with
1 same intensity resulting in a single signal.
0, 1
0 But we get two signals, this can be explained by
-1 considering zero field splitting

Two electron system

 +1

1
0, 1 Two signals
0 with different
0 intensities
ZFS
-1

Ext M F d2 configuration (oxo vanadium ion)

Usually the inorganic metal ions contain more than one unpaired
electrons resulting in ZEROFIELD splitting.
However, some of the organic molecules also exhibit zerofield splitting,
eg: Naphthalene.

h
Naphthalene Naphthalene*
UV
 Ground state Excited state 2 unpaired
electrons result in
LUMO – No ê LUMO – 1 ê
zerofield splitting
HOMO – 2 ê HOMO – 1 ê energy.

Table 1: number of unpaired electrons and total energy levels

present under external magnetic field
Number of Total ê ms Total ms values when
unpaired ê spin degeneracy is lost
1 ½ 1/2 +1/2, - 1/2
2 1 1 +1, 0, - 1
3 3/2 3/2 +3/2, +1/2, - ½, - 3/2
4 2 2 +2, +1, 0, - 1, -2
5 5/2 5/2 +5/2, +3/2, +1/2, - ½, - 3/2,
-5/2
Cr(III) complex: It is a d3 system containing 3 unpaired electrons.

From Number of Total ê ms Total ms values when

the === unpaired ê spin degeneracy is lost
above
table 3 3/2 3/2 +3/2, +1/2, - ½, - 3/2

 In the absence of ZFS all the electron spin states are

degenerate. Presence of zero field splitting removes
degeneracy of the spin states.
 However, when odd number of unpaired electrons are
present each energy level after zero field splitting is doubly
degenerate.
 Presence of this doubly degenerate condition in each energy
level after zero field splitting is known as Kramer’s degeneracy.
 ms

ms +3/2

ms 3/2
+1/2
1/2, 3/2
1/2
Abs ZFS
ZFS
& -1/2
Kramer’s
degeneracy
-3/2

Ext. M. F.

Cr (III) complex exhibiting zerofield splitting and Kramer’s degeneracy.

Three transitions at zerofield splitting occur.
 ms
[Mn(H2O)6]2+, [Mn(F)6]4- +5/2

ms
5/2 +3/2
ms

1/2, 3/2, 5/2 3/2

+1/2
Abs ZFS
1/2

ZFS
& -1/2
Kramer’s
degeneracy
-3/2

Ext. M. F. -5/2
Quadrupole Interactions:
The nucleus of paramagnetic ion is not necessarily spherically
symmetrical and may have an electrical quadrupole moment (Q).

The nucleus with I  1 gives nuclear quadrupole moment, which

is represented by eQ.
e – charge of the nucleus; Q – deviation from spherical shape.
When the nuclear quadrupole moment arises in the nucleus the
electron spin interacts with both nuclear spin magnetic momentum
and nuclear quadrupoar magnetic momentum.
 These interactions effect the esr signal as….
- The displacement of energy by equal amount.
- The NQM effect will be more towards the end of the spectrum
than the signals in the middle.
- The forbidden transitions are also observed in the spectrum.
- The isotopic effects can also be seen in the spectrum.

ms mI
-3/2
ms +1/2 -1/2
+1/2
1/2 +3/2
-3/2
-1/2 -1/2
+1/2
+3/2
Cu(II): I = 3/2

ESR spectra and quadrupolar interactions in

Cu(acac)2 in isomorphic diamagnetic Pd(acac)2 solid:
 Best examples are Cu(II) complexes. In the above complex Cu is in d 9
configuration. With n = 1, s = ½ and ms = 1/2.
 In the absence of external magnetic field the two spin states of the single
electron is degenerate.
 In the external magnetic field the degeneracy is lifted, lower energy level is
-1/2 and the upper energy level is +1/2.
 Each level is further split in to 4, due to hyperfine interaction. Transition
between these levels takes place according to selection rule ΔmI = 0.
 Thus 4 ESR signals are obtained. In addition to these four, forbidden
transitions are also appeared between the hyperfine signals. These forbidden
transitions are due to quadrupolar interactions.
 The separation towards ends is large than the separation in the middle
signals.
Thank you