Electron Paramagnetic Resonance A Practitioners Toolkit

Analy&cal
Methods in Chemistry
Analy&cal Methods in Chemistry

(CH-‐429)
Dr. Maheswaran Shanmugam
Email: eswar@chem.iitb.ac.in
Phone: 7187
What we are going to study?
Course details:
1. Electron paramagne@c resonance
2. Super conduc@ng Quantum Interference Device (SQUID)
3. Introduc@on to Op@cal methods
-‐ UV-‐Visible
-‐ Infra red
-‐ Fluorimetry
-‐ Atomic absorp@on
4. ScaQering of Radia@on -‐  Principle
-‐ Nephelometry -‐  Instrumenta&on
-‐ Turbidimetry -‐  Methods
-‐ Raman Spectroscopy -‐  Applica&ons
5. Electro-‐analy@cal methods
-‐ Cyclic voltammetry
-‐ Polarography
-‐ Amperometry
-‐ Conductometry
6. Thermogravimetry (TGA) and Differen@al thermal analysis (DTA)
7. Gas Chromatography and high performance liquid chromatography (HPLC)
Text Books and References
Text and Reference books:

1.  Electron paramagne@c Resonance: A prac@@oner’s tool kit
-‐  Marina Brustolon and Elio Giamell
2.  Electron Paramagne@c Resonance by John A Weil and James R. Bolton

3. NMR, NQR, EPR and Mossbauer spectroscopy in Inorganic Chemistry by
R. V. Parish
Electron Paramagen&c Resonance (EPR)
Electron Paramagne@c Resonance

Detects the unpaired electron in the
Electron Spin Resonance or
sample under inves@ga@on and its
Electro Magne@c Resonance
electronic structure around it
What is an EPR spectrum?

It is usually a plot of first deriva@ve of absorp@on of microwave frequency
radia@on against the magne@c field intensity.
Magne@c field (G)

Electron Paramagen&c Resonance (EPR)
EPR
Con@nuous wave method Pulsed method
Low intensity con@nuous irradia@on Short pulses of high power microwave
(microwave) of sample radia@ons are sent to the sample and
the sample response is recorded in the
absence of radia@on.
What are the main features of an EPR spectrum?
Main parameters and features of EPR spectrum:
1.  Posi@on of absorp@on: Magne@c field value at which the absorp@on takes place
2.  Number, Separa@on, rela@ve intensity of the lines
3.  Width and Shape of the line
Structure of the species under inves&ga&on

Their interac&on with environment
Dynamic process associated with it.
Magne&c moment of an electron
Defini@ve spin value of the vector, Sz = ± 1/2
These spin states are differ in orienta@on

of the angular momentum in space but
Representa@on of electron spin both spin state has same magnitude of
angular momentum vector angular momentum.
Origin of EPR spectra_electron spin in a magne&c field(Zeeman effect)
The existence of magne@c moment associated with the electron spin responsible
for the energy separa@on between the spin up and spin down
In the presence of magne&c field (B):
When B is parallel to z axis, then S will take the value of Sz
Electron spin in a magne&c field (Zeeman effect)
These two energy levels are degenerate in the absence of magne@c field
E
n
Spliing of electronic energy
e
level in the presence of
r
magne@c field called Zeeman
g
spliing or Zeeman Effect
y
B = 0 B > 0
In presence of Magne@c field, the degeneracy of these states will be lihed, based on
the alignment of the moments with the external magne@c field, one state will in
lower in energy and the other state will be higher in energy
Hence the spliing of energy levels depends on strength of the magne@c field.
Electron spin in a magne&c field (Zeeman effect)
Ms = +½
Ms

±½
ΔBpp
Energy
ΔE=hν=gβB
Ms = -‐½
B = 0 B > 0
Magne@c Field (B)
h Planck’s constant 6.626196 x 10-27 erg.sec
ν frequency (GHz or MHz)
g
β
g-factor (approximately 2.0023)
Bohr magneton (9.2741 x 10-21 erg.Gauss-1)
hν = gβB
B magnetic field (Gauss or mT) ν = (gβ/h)B = 2.8024 x B MHz

EPR is the resonant absorp@on of microwave radia@on for B = 3480 G ν = 9.75 GHz (X-‐band)
by paramagne@c systems in the presence of an applied for B = 420 G ν = 1.2 GHz (L-‐band)
magne@c field for B = 110 G ν = 300 MHz (Radiofre
Macroscopic collec&on of electron spins
Ø  Previously what we have described the situa@on for an isolated electron, however in
a real system the electrons will be in the order of 1010 or even more.
Ø  There will be interac@on between the electron or with environment
Ø  Not only that the electron will be confined in an orbital of an atom or a molecule
Even for the macroscopic system, in the absence of Magne&c field these electrons will be
equally distributed between the spin up state and spin down state (due to degeneracy of
these two states (spin up (α) and spin down(β)))
In the presence of magne@c field, distribu@on of electron between the spin down to
the spin up states are decided by the thermal equilibrium with the laice or
environment.
The ra@o between the number (N) of α spin to the β spin given by Boltzmann’s
distribu@on equa@on
kB = Boltzmann constant = 1.3806 × 10-‐23 J K

T = Absolute temperature of the laice.
Spin laTce relaxa&on
The equa@on becomes
Popula@on usually at lower energy state will be higher, hence the transi@on from β
spin state to α spin state occurs.
Due to con@nuous irradia@on of electromagne@c radia@on, it is possible to have
equal distribu@on of electron in spin down (β) state as well as spin up state (α). In
this situa@on, epr signal will saturate or disappears.

However, in reality even if you run the experiment con@nuously for long @me,
satura@on doesn’t occur due to spin-‐laice interac@on. Ie. The absorbed energy
will be lost due to interac@on with environment or laice.

This spin laice relaxa@on process occurs very rapidly which is usually reported as
inverse of the characteris@c @me T1 than the s@mulated emission.
Schema&c representa&on to explain spin laTce relaxa&on
Spin-‐laTce relaxa&on (longitudinal)
Spin-‐Laice relaxa@on @me (T1): This relates the characteris@c life&me of the electronic state
and is determined by the exchange of energy via thermal vibra&ons of the laTce.
Simplest individual resonance

line referred to Spin packet.
Spin-‐laTce relaxa&on rate (1/T1)
Spin-‐Laice relaxa@on @me (T1), which is very temperature dependent, measures the
characteris@c @me for recovery of the magne@za@on of the paramagne@c system along
the applied field direc@on aher equilibrium has been disturbed.
Direct process Raman Process Orbach Process

Direct process
This process is limited to electron-‐phonon interac@on where the phonon frequencies are
exactly equal the applied microwave frquency.
Mechanism: Modula@on of ligand field interacts with the vibra@onal modes of the laice
Raman process
Here, the phonon of frequency ν1 is scaQered by the paramagne@c center and emerge
with a different frequency ν2, the frequency difference being equal to the microwave
frequency.
Orbach process
Thermal ac@va@on from one electronic states of EPR transi@on and subsequent emission
or absorp@on of a phonon.
Spin-‐Spin relaxa&on (T2)
Spin-‐Spin relaxa@on is concerned with mutual spin flips caused by dipolar and exchange
interac@on between the assembly of spins making up the sample.
Physical significance: Spin-‐Spin interac@on is concentra&on dependent, temperature

independent and measures the @me taken for oscilla@ng component of the
magne@za@on in the plane normal to the applied magne@c field to get out-‐of-‐phase
with one another.
Due to spin-‐spin interac@ons, ohen the EPR lines obtained are broad, within that fine
structural details are buried. Example: Hyperfine interac@ons (which will give us the atoms
surrounded by the metal ions)
Observa&on of magne&c resonance
Epr resonance condi@on can be achieved by two ways
1. Under constant magne@c field, changing the frequency of microwave irradia@on intensity.
2. Under constant irradia@on of microwave of par@cular intensity, sweeping the magne@c
field.
Selec&on rule for

o b s e r v i n g t h e
EPR resonance
ΔMs = ± 1
Advantage of recording EPR in constant microwave frequency
Example 1:
Absorp&on First deriva&ve of absorp&on

Advantage of recording EPR in constant microwave frequency
Example 2:
Appears to be an isotropic
Spectrum. However due to spin-‐
orbit coupling (very small), the
resonance transi@on occurs very
c l o s e l y , r e s u l t s i n l i n e
broadening or line width
increases.
Due to increased quanta of

energy of microwave, the
distance between the peak
(resonance condi@on) also
increases linearly, results in high
EPR spectra of Dibenzothiophene radical recorded in resolu@on anisotropic spectra.
a) X-‐band (9.5 GHz) b) W-‐Band (95 GHz)
Instrumenta&on of CW-‐EPR
There are four important components in CW-‐EPR:

1. Microwave resonator
2. Microwave bridge
3. Magnet System
4. Control electronics
Microwave Resonator
Microwave resonator is the sample cell. ie This is where the sample under inves@ga@on
needs to be place (sample holder)

In addi@on, other two main purpose of microwave resonator is
Ø  To create sufficient microwave magne@c field at the sample posi@on to drive the transi@on
Ø  To efficiently convert the sample response into detectable microwave signal

Both of these factor depends on the value of quality factor Q
L-‐Band = 1 GHz
S-‐Band = ~3 GHz
X-‐Band = 9.5 GHz
Q-‐Band =~35 GHZ
νres = Resonance frequency of the resonator W-‐Band = 95 GHZ
Δν = Width of the resonance curve
Microwave Resonator
Microwave energy is stored in resonator leads to an enhancement in microwave

magne@c field (B1) and electric field (E1) compare to its free space value
B1 generated by microwave power P is given by
B1 = c × (Q×P)1/2
Where c = Conversion factor of a resonator the value ohen depends

resonator size (Smaller the resonator, larger the conversion factor
Also more importantly the peak to peak amplitude (ΔSpp) is

also depends on the Quality factor (Q)

ΔSpp α η × Q
Note:
ΔSpp α Q
ΔSpp α νres
Microwave Resonator
According to the above equa@on listed in the previous slide, the signal amplitude will
increases with increasing sample volume, along with Q. However, ohen Q factor is
lowered upon increasing the sample volume, hence the op@mum sample needs to be
used for corresponding instrument depends on the frequency
v  The benefits of resonator Q factor with respect to B1 (microwave magne@c
field) and the sensi@vity of the instrument (ie, resolu@on of peak to peak
separa@on)
v  Microwave frequency doesn’t have large window to sweep across, unlike
the external magne@c field
v  Hence, EPR is recorded with fixed microwave frequency with constant
intensity by sweeping the external magne&c field across.
Microwave Resonator
Microwave Electromagne@c radia@on Magne@c field component (B1) and

Electric field component (E1) (⊥ to each other)
Microwave Electric and magne@c field components
Magne@c field component (B1) Magne@c resonance transi@on

Electric field component (E1) Non-‐resonant microwave absorp@on
This causes decrease Through electric dipole

in Q factor and moment of the sample
undesired sample
hea@ng.
Hence EPR resonator has been designed based on electrodynamics principle
where the sample felt the B1 and minimizes the E1 at the sample posi@on
II. Microwave Bridge
Microwave frequencies are tradi@onally classified in term of a bands.
L-‐ Band 1 GHz Mainly used for biological sample and for live animals study (To
reduce the absorp@on of electric field component)
S-‐Band (3 GHz), X-‐Band (9.5 GHz), Q-‐Band (34 GHz), K-‐Band (24 GHz), W-‐Band (95 GHz)
Usually the higher frequency EPR instrument is used to get detailed insights about the
structure. Lower frequency (L and S band) instruments are used for biological applica@on.
“Cri&cal coupling”
The complete absorp@on of CW microwave power by the resonator is called Cri@cal coupling
or matching.
Reference arm
T o K e e p t h e
detector in Linear
response
Large and small

signals will be given
in correct amplitude
ra@o
When the magne@c field is swept through, resonance microwave energy is absorbed
by the sample that causes a change of the resonator Q factor. It is this change that
results in the reflec@on of microwaves from the resonator that in turn is registered as
the EPR signal.
Automa&c Frequency Control (AFC)
The change in the resonator Q factor, is EPR dispersion signal

The change in the matching condi@on of resonator (that is resonator reflects the
microwave signal) is EPR absorp@on

EPR absorp@on and EPR dispersion process appear in parallel.

AFC separates, more precisely eliminates the dispersion signal, only absorp@on signal is
detected.

Not only that AFC is linked to oscillator frequency which is locked to the resonator
frequency.

III. Magnet system
Magnet
Power supply unit Magnet system
Field sensor
Field Regulator
Lower than W-‐band (95 GHz), we can use electromagnets Magnet system
supplies the magne@c
W-‐band and above, we have to use superconduc@ng magnet field
X-‐Band (9.5 GHz) = 0.3 T or 3000 G

Q-‐Band (35 GHz) = ~1.3 T or 13 kG
Homogeneity of magne@c field at the sample posi@on is an another important
factor to be keep in mind
Magnet system
Hall sensor is installed in between the

Measuring and control the gap of electromagnet:
system to get the correct Ø  To give us accurate value of Magne@c
magne@c field value field posi@on, line width, separa@on
Ø  Mounted off center, to avoid the
field modula@on applied to resonator
Ø  Needs calibra@on (sample posi@on to
Hall sensor posi@on, since it is
Alterna&vely sample calibra&on can be done by using mounted offcenter)
standard sample: Ø  NMR Gauss meter used to calibrate
2,2-‐Diphenyl-‐1-‐picryl-‐hydrazyl (DPPH) = 2.0036 the Hall sensor with very high
Cr = 1.979 (Cr in MgO matrix)
3+ 3+
precision (10-‐6 to 10-‐7)
Mn2+ = 2.0011
Fundamentals
1.  g values
-‐  Spin-‐orbit coupling
-‐  Spin orbit coupling arising from the ground state (in-‐Phase)
-‐  Spin-‐orbit coupling arising from mixing of ground state with excited
states (Out-‐of-‐phase)
2.  Fine structure
-‐  Zero field spliing (Due to spin-‐orbit coupling and spin-‐spin interac@on)
3.  Hyperfine interac@on
4.  Isotropic and anisotropic EPR Spectra

Spin-‐orbit coupling basic concepts
To Explain the concept we will consider the transi@on metal ions
In gaseous ion all five d-‐orbitals are degenerate and splits in octahedral field as below
eg orbital
Δo
T2g orbital
Spin-‐orbit coupling basic concepts
Consider an electron in an orbital, where electron spins by itself (creates spin magne@c
moment), which revolves around the orbital (hence orbital angular momentum).
If total spin angular momentum (s) and total orbital

µtotal angular momentum (l) are independent or not
coupled with each other the resultant magne@c
moment of the system is given by
µorbital
µspin [1]
e-‐
However, in reality both spin and orbital angular
momentum are coupled together, ie. S and L are
no longer good quantum numbers, this requires
different quantum number “J” called total
The total angular momentum quantum angular momentum. The resultant magne@c
number takes the absolute values moment is given by
J = |L+S|..|L+S-‐1|.. |L-‐S|
g is Lande’s g-‐factor which has
defini@ve value for type of compounds
which depends on the spin and orbital
angular momentum
Rules for predic&ng the ground state Term Symbol (free gaseous ion)
General nota@on for term Symbol:

Where S is spin mul@plicity (S = 2s+1) [s = n/2]
L is the TERM corresponds to the highest L value
J is total angular momentum (J = |l+s|..|l+s-‐1|..|l-‐s|)
1)  For any electronic configura@on, states with highest S value ( S = n/2 where n =
number of unpaired electrons) is lowest in energy
2)  States with highest L will be in lowest energy
3)  J with |l -‐ s| value will be in lowest energy if the orbital is less than half filled
and J with |l + s| value will be in lowest energy if the orbital is greater than half
filled.
Example: L value TERM
d1 configura&on: 0 S
1 P
↑ 2 D
+2 +1 0 -‐1 -‐2 3 F
S = 2(1/2)+1 = 2 4 G
l = 1× (+2) = 2 5 H
J = l-‐s = 2-‐1/2 = 3/2 6 I
Work out for d2 to d10 configura&on?

Ground state Term Symbol for gaseous ion
m
ML=Σml
l
Configuration Example 2 1 0 -1 -2 L S Ground Term

1 3+ 2
d Ti 2 1/2 D
2 3+ 3
d V 3 1 F
3 3+ 4
d Cr 3 3/2 F
4 3+ 5
d Mn 2 2 D
5 2+ 6
d Mn 0 5/2 S
6 2+ 5
d Fe 2 2 D
7 2+ 4
d Co 3 3/2 F
8 2+ 3
d Ni 3 1 F
9 2+ 2
d Cu 2 1/2 D
General comparison of Term Symbol for gaseous ion d1-‐d9
ml ml
2 1 0 -2 ML S Example
-1 Configuration Ground Term
2 1 0 -1 -2 ML S
1 3+ 2
d2 1/2 Ti D 2 1/2
2 3+ 3 2
d3 1 V F 3 1
3 3+ 4 3
d3 3/2 Cr F
4
3 3/2
4 2+ 5
d2 2 Cr D 5 2 2
5 2+ 6
d0 5/2 Mn S 6 0 5/2
6
d2 2
2+ 5
Fe D 5 2 2
7 2+ 4 4
d3 3/2 Co F
3
3 3/2
8 2+ 3
d3 1 Ni F 2 3 1
9 2+ 2
d2 1/2 Cu D 2 1/2
Energies of J levels in V(III) ion
3λ
J =4 Energies of J states can be calculated by
3F
-‐λ
J =3
+2
+1
-‐4λ J =2 0
-‐1
In magne@c field -‐2
l = 3
s = 1 Energy difference between the J states is calculated by
J = |l+s| ..|l+s-‐1|..|l-‐s|
J = 4,3,2 ΔEJ, J+1= λ(J+1)
ΔE3,2 = 3 λ
ΔE4,3 = 4 λ
Microstates
“Microstates: In Terms of Molecular Energy Levels”,
In contrast, a microstate for a system is all about @me and the energy of the molecules in
that system. "In a system its energy is constantly being redistributed among its par@cles. In
liquids and gases, the par@cles themselves are constantly redistribu@ng in loca@on as well
as changing in the quanta (the individual amount of energy that each molecule has) due to
their incessantly colliding, bouncing off each other with (usually) a different amount of
energy for each molecule aher the collision.. Each specific way, each arrangement of the
energy of each molecule in the whole system at one instant is called a microstate."
hQp://entropysite.oxy.edu/microstate/index.html
Microstates in V(III) ion
For V(III) ion, d2 configura@on, hence n= 10 and r = 2
Total number of microstates available for d2 ion is = 10!/2!8! = 45
3λ To calculate number of microstate available for a par@cular

J =4
9 ground state term symbol is given by
(spin mul@plicity (2s + 1) × Orbital mul@plicity(2l +1))
3F For 3F = 3×7 = 21 states

21 (because s = 1 and l = 3)
-‐λ
J =3
7 +2
+1
-‐4λ J =2 0
5
-‐1
-‐2
In magne@c field
J split maintain the center of gravity ie the energy of the higher energy state (J=4) is
compensated by the sum of energies of lower energy state (J = 2 and 3)
9*3-‐7*1-‐5*4 = 0
Microstates for d2 ion
For a d2 ion maximum l value that we can obtain is = 4 and other possible l values are 3,2,1,0
l = 4
↑↓
+2 +1 0 -‐1 -‐2
l = 4; s = 0
1G
Microstates: Spin multiplicity (2s +1) × Orbital multiplicity (2l +1)

1× 9 = 9
l = 3
↑ ↑
+2 +1 0 -‐1 -‐2
l = 3; s = 1
3F
Microstates: Spin multiplicity (2s +1) × Orbital multiplicity (2l +1)

3× 7 = 21
Microstates for d2 ion
l = 2 l = 2
↑ ↑ ↑↓
+2 +1 0 -‐1 -‐2 +2 +1 0 -‐1 -‐2
l = 2; s = 1 l = 2; s = 0
3D 1D
Microstates: Spin multiplicity Microstates: Spin multiplicity

(2s +1) × Orbital multiplicity (2s +1) × Orbital multiplicity
(2l +1) (2l +1)
3× 5 = 15 1× 5 = 5
l = 1 l = 0
↑ ↑ ↑↓
+2 +1 0 -‐1 -‐2 +2 +1 0 -‐1 -‐2
l = 1; s = 1 l = 0; s = 0
3P 1S
Microstates: Spin multiplicity Microstates: Spin multiplicity

(2s +1) × Orbital multiplicity (2s +1) × Orbital multiplicity
(2l +1) (2l +1)
3× 5 = 15 1× 5 = 5
Rela&onship between Term symbols and Tanabe-‐Sugano diagram
1G
3F
3D 1D
3P
1S
Orbital contribu&on to the magne&c moment
When Orbital contribu@on arises ?

In order that an electron can have orbital angular momentum, it must be possible
to transform the orbital that it occupies into an exactly equivalent and degenerate
orbital by rota<on.

The electron is then effec@vely rota@ng about the axis used for the orbital rota@on.
(the circula@on of an electron around the nucleus is like the circula@on of a current
through the turns of a solenoid)
Spin-‐Orbit coupling in transi&on metal octahedral complexes
The degenerate t2g orbitals (dxy, dxz, dyz) can be interconverted by 90° rota@ons
eg orbital
Δo
T2g orbital
C4
Thus, an electron in a t2g orbital can

C4 contribute to orbital angular
momentum
e.g. the dxz orbital is transformed into the dyz orbital by a rota@on of 90° about the z-‐axis –
during this rota@on the electron is orbi@ng the nucleus
Is spin-‐orbit coupling will be there in eg orbital in Oh?
The eg orbitals cannot be interconverted by rota@on due to their nature of shape
of orbital
The unpaired electron in eg orbital cannot contribute to spin-‐orbit coupling
Is t2g to eg inter-‐conversion possible by rota&on?
Yes. Inter conversion is possible.
However, in octahedral field or any

ligand field, t 2g and e g orbital
separated by Δ0 (in Oh field), hence
the mixing of dxy and dx2-‐y2 will depend
on the energy gap between these two
level.
dxy / dx2-‐y2 orbital mo@on about z axis

dxz / dyz orbital mo@on about z axis
dxz / dxy orbital mo@on about x axis
dyz / dxy orbital mo@on about y axis
Orbital contribu&on to the magne&c moment: High spin octahedral dn
ions
Think of possible t2g electron arrangements
d1
dxz dyz dxy dxz dyz dxy dxz dyz dxy
Possible t2g arrangements = 3 d1 e.g. Ti(III)

Orbital contribu@on = YES
d2
Possible t2g arrangements = 3

Orbital contribu@on = yes d2 e.g. V(III)
ions
But, electrons in t2g orbitals will not always contribute to orbital
angular momentum
e.g. consider octahedral Cr(III) d3, t2g3
an electron in the dxz orbital cannot by rota@on be placed in e.g.
the dyz orbital because this orbital already contains an electron
with the same spin as the incoming electron
dxz dyz dxy dxz dyz dxy
Therefore, there is only one possible t2g arrangement,

and NO
orbital angular momentum
ions

d4 high spin t2g half-‐filled

dxz dyz dxy
Possible t2g arrangements = 1 d4 e.g. Cr(II)

Orbital contribu@on = NO
d5 high spin t2g half-‐filled

dxz dyz dxy
Possible t2g arrangements = 1 d5 e.g. Mn(II),

Orbital contribu@on = NO Fe(III)
ions

d6 high spin
Possible t2g arrangements = 3 d6 e.g. Fe(II)

d7 high spin
Possible t2g arrangements = 3 d7 e.g. Co(II)

ions

Ni(II) d8 t2g filled
Possible t2g arrangements = 1 d8 e.g. Ni(II)

Cu(II) d9 t2g filled
Possible t2g arrangements = 1 d9 e.g. Cu(II)

Orbital contribu&on to the magne&c moment: Contribu&on due to
excited state
think of possible t2g electron arrangements

t2g not comp.

Ni(II) d8 t2g filled
filled
Excited state
Orbital contribu@on = NO (due to ground state)
d8 high spin ES

μexp > μs for Oct. Ni2+

How to dis&nguish Ni Td and Oh complexes?
Therefore for Oh Ni(II) the magne&c moments are larger if the GS-‐ES gap is small.
BUT FOR Tetrahedral Ni(II) situa&on is en&rely different ….
d8 HS Tetrahedral

Μexp Oh Ni(II) is smaller than Μexp Td Ni(II)
Exp. NiCl42-‐, Ni(HMPA)42+ (HMPA=hexamethyl phosphoramide)

have magne@c moment larger than 4 BM.
(larger the distor@on smaller the magne@c moment )

USEFUL IN DISCRIMINATING Oh vs Td structures.
How does this spin-‐orbit coupling affect the g-‐value?
Ø  For free or isolated electron, the g-‐value is determined as 2.0023
First
deriva@ve Absorp@on Measure B (“resonance field”) for
given applied υ.

Magne@c field (G)

Ø  Presence of orbital angular momentum can interact with spin angular momentum
construc@vely or it may oppose each other. In such cases, the observed magne@c
moment either higher than or lower than (respec@vely) compare to free electron.
Hence there will be change in g-‐value of complex.
Ø  Magne@c field in linear rela@onship with magne@c moment, ie larger the moment,
spliing of moment in magne@c field will be higher.
Ø  From g-‐value we can deduce the electronic environment of an atom or ion.
What controls g-‐value?
Where
a denotes covalency, usually a2 will be < 1 (if an unpaired electron
delocalized, the spin-‐orbit coupling will be reduced.
λ  = Spin orbit coupling constant
ΔE = Energy gap between the orbitals
(Bigger ΔE → less mixing → smaller shih of g from ge. Note ΔE
corresponds to an electronic dd transi&on!)
n = depends on the iden@ty of orbitals which are being mixed
λ  = Posi@ve for less than half filled orbitals

λ  = Nega@ve for more than half filled orbital
Hence, the g-‐value is higher than the free electron g-‐value (ge) for more than half filled
electronic configura@on and the same will be less the free electron g-‐value (ge) for less than
half filled d-‐orbital.
Predic&on of n value from Magic Pentagon

Electron Paramagnetic Resonance A Practitioners Toolkit

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Electron Paramagnetic Resonance A Practitioners Toolkit

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Analy&cal

Methods in Chemistry

Analy&cal Methods in Chemistry

Text and Reference books:

Electron Paramagne@c Resonance

What is an EPR spectrum?

Magne@c ﬁeld (G)

Con@nuous wave method Pulsed method

Structure of the species under inves&ga&on

Deﬁni@ve spin value of the vector, Sz = ± 1/2

These spin states are diﬀer in orienta@on

In the presence of magne&c ﬁeld (B):

kB = Boltzmann constant = 1.3806 × 10-­‐23 J K

The equa@on becomes

Simplest individual resonance

Direct process Raman Process Orbach Process

Physical signiﬁcance: Spin-­‐Spin interac@on is concentra&on dependent, temperature

Selec&on rule for

Absorp&on First deriva&ve of absorp&on

Due to increased quanta of

There are four important components in CW-­‐EPR:

Microwave energy is stored in resonator leads to an enhancement in microwave

B1 generated by microwave power P is given by

Where c = Conversion factor of a resonator the value ohen depends

Also more importantly the peak to peak amplitude (ΔSpp) is

Microwave Electromagne@c radia@on Magne@c ﬁeld component (B1) and

Microwave Electric and magne@c ﬁeld components

Magne@c ﬁeld component (B1) Magne@c resonance transi@on

This causes decrease Through electric dipole

Microwave frequencies are tradi@onally classiﬁed in term of a bands.

Large and small

X-­‐Band (9.5 GHz) = 0.3 T or 3000 G

Hall sensor is installed in between the

3. Hyperﬁne interac@on

4. Isotropic and anisotropic EPR Spectra

If total spin angular momentum (s) and total orbital

General nota@on for term Symbol:

Work out for d2 to d10 conﬁgura&on?

Configuration Example 2 1 0 -1 -2 L S Ground Term

3λ To calculate number of microstate available for a par@cular

3F For 3F = 3×7 = 21 states

Microstates: Spin multiplicity (2s +1) × Orbital multiplicity (2l +1)

Microstates: Spin multiplicity (2s +1) × Orbital multiplicity (2l +1)

Microstates: Spin multiplicity Microstates: Spin multiplicity

Microstates: Spin multiplicity Microstates: Spin multiplicity

When Orbital contribu@on arises ?

Thus, an electron in a t2g orbital can

Yes. Inter conversion is possible.

However, in octahedral ﬁeld or any

dxy / dx2-­‐y2 orbital mo@on about z axis

Possible t2g arrangements = 3 d1 e.g. Ti(III)

Possible t2g arrangements = 3

dxz dyz dxy dxz dyz dxy

Therefore, there is only one possible t2g arrangement,

d4 high spin t2g half-­‐ﬁlled

Possible t2g arrangements = 1 d4 e.g. Cr(II)

d5 high spin t2g half-­‐ﬁlled

Possible t2g arrangements = 1 d5 e.g. Mn(II),

Possible t2g arrangements = 3 d6 e.g. Fe(II)

Possible t2g arrangements = 3 d7 e.g. Co(II)

Ni(II) d8 t2g ﬁlled

Possible t2g arrangements = 1 d8 e.g. Ni(II)

Cu(II) d9 t2g ﬁlled

kB = Boltzmann constant = 1.3806 × 10-‐23 J K

Physical signiﬁcance: Spin-‐Spin interac@on is concentra&on dependent, temperature

There are four important components in CW-‐EPR:

X-‐Band (9.5 GHz) = 0.3 T or 3000 G

3.  Hyperﬁne interac@on

4.  Isotropic and anisotropic EPR Spectra

dxy / dx2-‐y2 orbital mo@on about z axis

d4 high spin t2g half-‐ﬁlled

d5 high spin t2g half-‐ﬁlled

Exp. NiCl42-‐, Ni(HMPA)42+ (HMPA=hexamethyl phosphoramide)

λ  = Posi@ve for less than half ﬁlled orbitals