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Electron Paramagnetic Resonance A Practitioners Toolkit
Electron Paramagnetic Resonance A Practitioners Toolkit
EPR
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
The
existence
of
magne@c
moment
associated
with
the
electron
spin
responsible
for
the
energy
separa@on
between
the
spin
up
and
spin
down
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
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.
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.
B1 = c × (Q×P)1/2
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
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
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
Homogeneity
of
magne@c
field
at
the
sample
posi@on
is
an
another
important
factor
to
be
keep
in
mind
Magnet
system
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)
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).
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
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
-‐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
l
=
3
↑
↑
+2
+1
0
-‐1
-‐2
l = 3; s = 1
3F
l
=
1
l
=
0
↑
↑
↑↓
+2
+1
0
-‐1
-‐2
+2
+1
0
-‐1
-‐2
l = 1; s = 1
l = 0; s = 0
3P
1S
1G
3F
3D 1D
3P
1S
Orbital
contribu&on
to
the
magne&c
moment
(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
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?
d1
dxz
dyz
dxy
dxz
dyz
dxy
dxz
dyz
dxy
d2
dxz
dyz
dxy
dxz
dyz
dxy
dxz
dyz
dxy
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
d6
high
spin
dxz
dyz
dxy
dxz
dyz
dxy
dxz
dyz
dxy
d7 high spin
Excited
state
Possible
t2g
arrangements
=
1
Orbital
contribu@on
=
NO
(due
to
ground
state)
d8 HS Tetrahedral
First
deriva@ve
Absorp@on
Measure
B
(“resonance
field”)
for
given
applied
υ.
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