Zero-field splitting (zfs) is the removal spin microstate degeneracy for systems with S > 1/2 in the

absence of an applied field. That is, the degeneracy is removed as a consequence of molecular electronic
structure and/or spin density distribution. For odd-electron systems, axial zfs (the D zfs parameter)
removes the microstate degeneracy and produces Kramers doublets. Rhombic zfs (the E zfs
parameter) splits the Kramers doublets. Zero-field splitting causes magnetic anisotropy, and has
profound effects on magnetic properties. For example, magnetic hardness ( the width of a hysteresis
loop) is related to the magnetoanisotropy. At the molecular level, understanding zfs is essential for
rational design of single-molecule magnets since the energy barrier separating the +m
s
and -m
s
microstates is equal to |S
2
D|.
1
The energies of spin microstates in units of D are given by equation 1,
assuming E = 0.
E D S
S S
m z
s
=
+ ( ) |
|
|
|
|
|

2
1
3
(1)
Energy level spacings for S = 1 to 5/2 are shown below for D < 0.
S = 1 S = 3/2 S = 2 S = 5/2
m
s
=1
m
s
=0
m
s
=3/2
m
s
=1/2
2D
m
s
=2
m
s
=1
3D
m
s
=0
m
s
=5/2
m
s
=3/2
4D
m
s
=1/2
2D
D
D
Orbital angular momentum can be of primary contributor to zfs, and can make the zfs quite large (1-
10 cm
-1
)compared to spin-dipolar contributions (10
-3
- 10
-1
cm
-1
). There are two scenarios in which
orbital angular momentum manifests itself in zfs: in-state orbital angular momentum (e.g., orbital T states
in O
h
symmetry), and out-of state orbital angular momentum (e.g., spin-orbit mixing of certain excited
states into the ground state).
In-state orbital angular momentum can give rise to very large zfs. However, in such cases, the zfs
parameters lose their traditional meanings. Consider the d
2
electron configuration at O
h
symmetry. The
ground state is
3
T
1g
. At O
h
symmetry, the spin-orbit coupling operator (which always transforms as the
rotations) transforms at t
1g
. Thus, spin-orbit coupling breaks the triplet microstate degeneracy (S = 1; m
s
=
1, 0) by coupling to the degenerate orbital states to give rise to A
1g
, E
g
, T
1g
, and T
2g
states.
e
g
t
2g
d
2
at O
h
symmetry: t
2g
2
3
T
1g
Ground state
orbital degeneracy = 3
spin microstate degeneracy = 3
Spin-Orbit
Coupling
A
1g
E
g
T
2g
T
1g
Spin-Orbit Coupling Splits
spin multiplet by mixing
with orbital multiplet.
"ZFS" large, but zfs
parmeters D and E lose
their meaning.
Out-of state orbital angular momentum can also give rise to zfs, but not alone. Consider the d
8
electron configuration at O
h
symmetry. The ground state is
3
A
2g
, with low-lying
3
T
2g
and
3
T
1g
excited
states. Both excited states have orbital angular momentum, but the interaction that mixes these states into
the ground state must transform as A
2g
T
1g
= T
2g
or as A
2g
T
2g
= T
1g
. Since the spin-orbit coupling
operator transforms as t
1g
, then spin-orbit coupling can mix the
3
T
2g
state into the ground state. However,
this mixing does not break the spin degeneracy of the ground state since A
2g
T
1g
= T
2g
, and the
degeneracy is retained.
e
g
t
2g
d
8
at O
h
symmetry: t
2g
6
e
g
2
3
A
2g
Ground state
orbital degeneracy = 1
spin microstate degeneracy = 3
Spin-Orbit
Coupling
T
2g
Spin-Orbit Coupling does
not remove degeneracy
of spin multiplet (D = 0)
Excited state
orbital degeneracy =3
spin microstate degeneracy = 3
3
T
2g
Spin-Orbit
Coupling
A
1g
E
g
T
2g
T
1g
Now consider the effect of a ligand field distortion. A trigonal distortion lowers the symmetry to D
3d
,
and splits the ground T
1g
state into an A
2g
and an E
g
. Any distortion that removes the degeneracy of t
1g
will work. Thus, the spin-orbit coupling plus the distortion combine as perturbations to allow the ground
state feel the excited state splitting. The result is zero-field splitting.
3
A
2g
Ground state
orbital degeneracy = 1
spin microstate degeneracy = 3
Spin-Orbit
Coupling
T
2g
Spin-Orbit Coupling does
not remove degeneracy
of spin multiplet (D = 0)
Excited state
orbital degeneracy =3
spin microstate degeneracy = 3
3
T
2g
Spin-Orbit
Coupling
A
1g
E
g
T
2g
T
1g
Trigonal distortion
Trigonal distortion
E
g
A
2g
A
1g
2A
2g
3E
g
Spin-Orbit Coupling plus
distortion to D
3d
results in
zfs (D > 0 shown)
Note that the order of spin-orbit coupling and distortion is irrelevant. The following illustrates.
3
A
2g
3
T
2g
O
h
+ Spin-Orbit
Coupling
(D = 0)
+ Distortion
(D
3d
; (D 0)
+ Spin-Orbit
Coupling
(D 0)
3
A
2g
T
2g A
2g
E
g
E
g
A
1g
T
1g
T
2g
+ Distortion
(D
3d
; D = 0)
A
2g
E
g
A
1g
2A
2g
3E
g
3
A
2g
3
E
g
A
1g
2A
2g
3E
g
Diagrams like those on the last page can be drawn for any orbital singlet state with S > 1/2. The
issues are (1) the symmetry, (2) the number, and (3) energies of excited states. For example, Cr
III
has only
one low-lying excited state that can impart orbital angular momentum to the ground state via spin-orbit-
induced configuration interaction. However, this state is high-lying, so the mixing is weak and |D| < 1
cm
-1
. However, distorted six- and five-coordinate Mn
III
has three low-lying states that can mix with the
ground state, so the mixing is relatively strong and |D| > 1 cm
-1
. However, even when more than one
excited state contributes to ground state zfs, different excited states can provide contributions to D of
opposite signs. The sign of each contribution arises from the particular spin-orbit coupling matrix
elements.
As an example, consider the diagrams below for five-coordinate Mn
III
at C
4v
symmetry.
2
5
E
g
3
T
1g
O
h
5
T
2g
+ Tetragonal
Distortion
(C
4v
)
5
B
1
5
E
5
B
2
3
A
2
3
E
5
A
1

1
Electron
Configuration
(b
2
1
e
2
a
1
1
)
(b
2
1
e
2
b
1
1
)
(b
2
1
e
1
a
1
1
b
1
1
)
(e
2
a
1
1
b
1
1
)
(b
2
2
e
2
)
(b
2
1
e
3
)
At C
4v
,
rotations
transform as
a
2
+ e
Hole
d
x
2
-y
2
d
z
2
d
xz,yz
d
xy
d
xz,yz
---
D
3D
M
s
= 2
M
s
= 1
M
s
= 0
d
xy
d
xz,yz
d
z
2
d
x
2
-y
2
Ground
Configuration

b
2
e
a
1
b
1
Quintet M
s
spacings
The ground-state term symbol is
5
B
1
. Excited states can mix with the ground state and give rise to zfs.
The expression for the axial zfs in the
5
B
1
ground state of Mn
III
(at C
4v
symmetry) is given by equation 1:
D= +

( )
|
|
|
|
|
|
|
|
|
|

2
3
1
4 4 1

(1)
Equation 1 comes from evaluating the mixing of every M
S
level for each excited state with each M
S
level of the
5
B
1
ground state. As such, there are 145 terms to consider! However, since B
1
(a
2
+ e) = B
2
+ E, only three of the five excited states will mix with the
5
B
1
ground state via spin-orbit coupling. These
are the
5
E, the
5
B
2
, and the
3
E. Now, were down to 105 terms. Fortunately, as will be shown, many of
these need not be computed. So, lets derive equation 1 beginning with writing down the orbital functions
for each electronic state.
5
B
1
= d d d d
xy xz yz
z2
(2)
5
A
1
=

d d d d
xy xz yz
x y 2 2
(3)
5
E=

d d d d
xy xz
z x y 2 2 2
(4)
and =

d d d d
xy yz
z x y 2 2 2
(5)
5
B
2
=

d d d d
xz yz
x y z 2 2 2
(6)
3
A
2
= d d d d
xy xy xz yz
(7)
3
E= d d d d
xy xz xz yz
(8)
and = d d d d
xy yz yz xz
Now lets write down the M
S
wavefunctions for each electronic state. For the
5
B
1
(ground state), we have:
M xy xz yz z
s
=
[ |
2
2
; (9)
M xy xz yz z xy xz yz z xy xz yz z xy xz yz z
s
= + + +
[ |
1
1
2
2 2 2 2
; (10)
M xy xz yz z xy xz yz z xy xz yz z xy xz yz z xy xz yz z xy xz yz z
s
= + + + + +
[ |
0
1
6
2 2 2 2 2 2
; (11)
M xy xz yz z xy xz yz z xy xz yz z xy xz yz z
s
= + + +
[ |
1
1
2
2 2 2 2
; (12)
M xy xz yz z
s
=
[ |
2
2
; (13)
For
5
B
2
we have:
M x y xz yz z
s
=
[ |
2
2 2 2
; (14)
M x y xz yz z x y xz yz z x y xz yz z x y xz yz z
s
= + + +
[ |
1
1
2
2 2 2 2 2 2 2 2 2 2 2 2
; (15)
M
x y xz yz z x y xz yz z x y xz yz z
x y xz yz z x y xz yz z x y xz yz z
s
=
+ + +
+ +
|
|
|
|
|
|
|
|
0
1
6
2 2 2 2 2 2 2 2 2
2 2 2 2 2 2 2 2 2
; (16)
M x y xz yz z x y xz yz z x y xz yz z x y xz yz z
s
= + + +
[ |
1
1
2
2 2 2 2 2 2 2 2 2 2 2 2
; (17)
M x y xz yz z
s
=
[ |
2
2 2 2
; (18)
For
3
E we get,
M xy xz yz yz
s
=
[ |
1; (19)
M xy xz yz yz xy xz yz yz
s
= +
[ |
0
1
2
; (20)
M xy xz yz yz
s
=
[ |
1; (21)
and:
M xy xz yz xz
s
=
[ |
1; (22)
M xy xz yz xz xy xz yz xz
s
= +
[ |
0
1
2
; (23)
M xy xz yz xz
s
=
[ |
1; (24)
For
5
E:
M xy xz x y z
s
=
[ |
2
2 2 2
; (25)
M xy xz x y z xy xz x y z xy xz x y z xy xz x y z
s
= + + +
[ |
1
1
2
2 2 2 2 2 2 2 2 2 2 2 2
; (26)
M
xy xz x y z xy xz x y z xy xz x y z
xy xz x y z xy xz x y z xy xz x y z
s
=
+ +
+ + +
|
|
|
|
|
|
|
|
0
1
6
2 2 2 2 2 2 2 2 2
2 2 2 2 2 2 2 2 2
; (27)
M xy xz x y z xy xz x y z xy xz x y z xy xz x y z
s
= + + +
[ |
1
1
2
2 2 2 2 2 2 2 2 2 2 2 2
; (28)
M xy xz x y z
s
=
[ |
2
2 2 2
; (29)
and:
M xy yz x y z
s
=
[ |
2
2 2 2
; (30)
M xy yz x y z xy yz x y z xy yz x y z xy yz x y z
s
= + + +
[ |
1
1
2
2 2 2 2 2 2 2 2 2 2 2 2
; (31)
M
xy yz x y z xy yz x y z xy yz x y z
xy yz x y z xy yz x y z xy yz x y z
s
=
+ +
+ + +
|
|
|
|
|
|
|
|
0
1
6
2 2 2 2 2 2 2 2 2
2 2 2 2 2 2 2 2 2
; (32)
M xy yz x y z xy yz x y z xy yz x y z xy yz x y z
s
= + + +
[ |
1
1
2
2 2 2 2 2 2 2 2 2 2 2 2
; (33)
M xy yz x y z
s
=
[ |
2
2 2 2
; (34)
As shown in the figure on page 1, for a quintet state, D is given by the energy gap between the M
s
= 1
and M
s
= 0 microstates. Therefore, only matrix elements that include these
5
B
1
M
s
levels need to be
calculated. Strictly speaking, that means that we have to compute only 42 terms. As youll see,
symmetry demands that many of these terms make the same contribution.
For M
S
= 1 of
5
B
1
we have:
M xy xz yz z xy xz yz z xy xz yz z xy xz yz z
s
= + + +
[ |
1
1
2
2 2 2 2
; (10)
For
5
B
1
mixing with
5
B
2
(only l
z
s
z
)
M x y xz yz z
s
=
[ |
2
2 2 2
; (14)
gives
1
2
1
2
0
2 2 2 2
xy l s x y xy l x y s
z z

[ |
=
[ |
= (35)
M x y xz yz z x y xz yz z x y xz yz z x y xz yz z
s
= + + +
[ |
1
1
2
2 2 2 2 2 2 2 2 2 2 2 2
; (15)
gives
1
4
3
1
4
3
1
4
2
1
2
3 2
1
2 2
2 2 2 2
2 2 2 2
xy l s x y xy l s x y
xy l x y s xy l x y s i i
i
z z z z
+
[ |
= +
[ |
= ( )
[
\

)
+ ( ) +
[
\

)
|
|
|
|
|
|
=
(36)
M
x y xz yz z x y xz yz z x y xz yz z
x y xz yz z x y xz yz z x y xz yz z
s
=
+ +
+ + +
|
|
|
|
|
|
|
|
0
1
6
2 2 2 2 2 2 2 2 2
2 2 2 2 2 2 2 2 2
; (16)
gives
1
2
1
2
0
2 2 2 2
xy l s x y xy l x y s
z z

[ |
=
[ |
= (37)
M x y xz yz z x y xz yz z x y xz yz z x y xz yz z
s
= + + +
[ |
1
1
2
2 2 2 2 2 2 2 2 2 2 2 2
; (17)
gives 0 (38)
M x y xz yz z
s
=
[ |
2
2 2 2
; (18)
gives 0 (39)
For M
s
= 1 of
5
B
1
mixing with
3
E

(only l
x
s
x
and l
y
s
y
) we have:
M xy xz yz z xy xz yz z xy xz yz z xy xz yz z
s
= + + +
[ |
1
1
2
2 2 2 2
; (10)
For
3
E:
M xy xz yz yz
s
=
[ |
1; (19)
gives
1
2
1
2
0
2 2
z l s yz z l yz s
x x

[ |
=
[ |
= (40)
M xy xz yz yz xy xz yz yz
s
= +
[ |
0
1
2
; (20)
gives
1
2 2
2
1
2 2
2
1
2
3
1
2
3
8
2 2
z l s yz z l yz s i i
x x

[ |
=
[ |
=
( )
[
\

)
|
|
|
|
|
|
= (41)
M xy xz yz yz
s
=
[ |
1; (21)
gives 0 (42)
and:
M xy xz yz xz
s
=
[ |
1; (22)
gives
1
2
1
2
0
2 2
xz l s z xz l z s
y y

[ |
=
[ |
= (43)
M xy xz yz xz xy xz yz xz
s
= +
[ |
0
1
2
; (23)
gives
1
2 2
2
1
2 2
2
1
2
3
2
3
8
2 2
z l s xz z l xz s i
i
y y

[ |
=
[ |
=
( )

[
\

)
|
|
|
|
|
|
= (44)
M xy xz yz xz
s
=
[ |
1; (24)
gives 0 (45)
For M
s
= 1 of
5
B
1
mixing with
5
E

(only l
x
s
x
and l
y
s
y
), we have:
M xy xz yz z xy xz yz z xy xz yz z xy xz yz z
s
= + + +
[ |
1
1
2
2 2 2 2
; (10)
For
5
E:
M xy xz x y z
s
=
[ |
2
2 2 2
; (25)
gives
1
2
1
2
1
2
1
2 4
2 2 2 2
yz l s x y yz l x y s i
i
x x

[ |
=
[ |
= ( )
[
\

)
|
|
|
|
|
|
= (46)
M xy xz x y z xy xz x y z xy xz x y z xy xz x y z
s
= + + +
[ |
1
1
2
2 2 2 2 2 2 2 2 2 2 2 2
; (26)
gives
1
4
3 3 0
2 2 2 2 2 2 2 2
x y l s yz x y l s yz x y l yz s x y l yz s
x x x x
+
[ |
= +
[ |
= (47)
M
xy xz x y z xy xz x y z xy xz x y z
xy xz x y z xy xz x y z xy xz x y z
s
=
+ +
+ + +
|
|
|
|
|
|
|
|
0
1
6
2 2 2 2 2 2 2 2 2
2 2 2 2 2 2 2 2 2
; (27)
gives
1
2 6
3
1
2 6
3
1
2 6
3
1
2 2
3
8
2 2 2 2
yz l s x y yz l x y s i
i
x x

[ |
=
[ |
= ( )
[
\

)
|
|
|
|
|
|
= (48)
M xy xz x y z xy xz x y z xy xz x y z xy xz x y z
s
= + + +
[ |
1
1
2
2 2 2 2 2 2 2 2 2 2 2 2
; (28)
gives 0 (49)
M xy xz x y z
s
=
[ |
2
2 2 2
; (29)
gives 0 (50)
and, M
s
= 1 of
5
B
1
:
M xy xz yz z xy xz yz z xy xz yz z xy xz yz z
s
= + + +
[ |
1
1
2
2 2 2 2
; (10)
with
5
E:
M xy yz x y z
s
=
[ |
2
2 2 2
; (30)
gives
1
2
1
2
1
2 2
1
4
2 2 2 2
xz l s x y xz l x y s i
i
y y

[ |
=
[ |
= ( )
[
\

)
|
|
|
|
|
|
= (51)
M xy yz x y z xy yz x y z xy yz x y z xy yz x y z
s
= + + +
[ |
1
1
2
2 2 2 2 2 2 2 2 2 2 2 2
; (31)
gives 0 (52)
M
xy yz x y z xy yz x y z xy yz x y z
xy yz x y z xy yz x y z xy yz x y z
s
=
+ +
+ + +
|
|
|
|
|
|
|
|
0
1
6
2 2 2 2 2 2 2 2 2
2 2 2 2 2 2 2 2 2
; (32)
gives
1
2 6
3
1
2 6
3
1
2 6
3
2
1
2
3
8
2 2 2 2
xz l s x y xz l x y s i
i
y y

[ |
=
[ |
= ( )
[
\

)
|
|
|
|
|
|
= (53)
M xy yz x y z xy yz x y z xy yz x y z xy yz x y z
s
= + + +
[ |
1
1
2
2 2 2 2 2 2 2 2 2 2 2 2
; (33)
gives 0 (54)
M xy yz x y z
s
=
[ |
2
2 2 2
; (34)
gives 0 (55)
The net energy lowering of M
s
= 1 of
5
B
1
( E) is given by a second order correction. The
numerator of the second-order correction is a summation of each matrix element computed above
multiplied by its complex conjugate, and the denominator is the excited state energy. Thus, the
energy lowering is:
E(M
s
= 1 of
5
B
1
) =

( )

( )

+
[
\
|

)
j

[
\
|

)
j
+
[
\
|

)
j

[
\
|
|
|
|

)
j
j
j
j
+

[
\

)
[
\

)
+
[
\
|

)
j
[
\
|

)
j
+

2
5
2
5
1
2
3 5
1
2 2
3
8
3
8
3
8 4 4 2
3
8 2
3
8
i i
E B E B
i i
E E E B
i i i i
( ) ( ) ( ) ( )
11
4
1
2
3
8
2
2
5 5
1
[
\

)
+
[
\
|

)
j

[
\
|
|
|
|

)
j
j
j
j
|
|
|
|
|
|
|
|
|
|
|
|
|
|
E E E B ( ) ( )
=

|
|
|
|
|
|
|
|

2
5
2
5
1
3 5
1
5 5
1
1
4
6
8
5
16
E B E B E E E B E E E B ( ) ( ) ( ) ( ) ( ) ( )
(56)
Now to calculate the corresponding terms for M
s
= 0 of
5
B
1
:
M xy xz yz z xy xz yz z xy xz yz z xy xz yz z xy xz yz z xy xz yz z
s
= + + + + +
[ |
0
1
6
2 2 2 2 2 2
; (11)
For
5
B
1
mixing with
5
B
2
(only l
z
s
z
),
M x y xz yz z
s
=
[ |
2
2 2 2
; (14)
gives 0 (57)
M x y xz yz z x y xz yz z x y xz yz z x y xz yz z
s
= + + +
[ |
1
1
2
2 2 2 2 2 2 2 2 2 2 2 2
; (15)
gives
1
2 6
3
1
2 6
3 0
2 2 2 2
x y l s xy x y l xy s
z z

[ |
=
[ |
= (58)
M
x y xz yz z x y xz yz z x y xz yz z
x y xz yz z x y xz yz z x y xz yz z
s
=
+ +
+ + +
|
|
|
|
|
|
|
|
0
1
6
2 2 2 2 2 2 2 2 2
2 2 2 2 2 2 2 2 2
; (16)
gives
1
6
3 2
1
6
3 3
2 2 2 2 2 2 2 2
x y l s xy x y l s xy x y l xy s x y l xy s
z z z z
+
[ |
= +
[ |

= ( )
[
\

)
+ ( )
[
\

)
|
|
|
|
|
|
= ( ) + ( )
[ |
=
1
6
3 2
1
2
3 2
1
2
1
6
3 3 0 i i i i (59)
M x y xz yz z x y xz yz z x y xz yz z x y xz yz z
s
= + + +
[ |
1
1
2
2 2 2 2 2 2 2 2 2 2 2 2
; (17)
gives
1
2 6
3
1
2 6
3 0
2 2 2 2
x y l s xy x y l xy s
z z

[ |
=
[ |
= (60)
M x y xz yz z
s
=
[ |
2
2 2 2
; (18)
gives 0 (61)
For M
s
= 0 of
5
B
1
mixing with
3
E

(only l
x
s
x
and l
y
s
y
):
M xy xz yz z xy xz yz z xy xz yz z xy xz yz z xy xz yz z xy xz yz z
s
= + + + + +
[ |
0
1
6
2 2 2 2 2 2
; (11)
For
3
E:
M xy xz yz yz
s
=
[ |
1; (19)
gives
1
6
1
6
1
6
3
1
2
1
8
2 2
z l s yz z l yz s i i
x x

[ |
=
[ |
=
( )
[
\

)
|
|
|
|
|
|
= (62)
M xy xz yz yz xy xz yz yz
s
= +
[ |
0
1
2
; (20)
gives
1
12
2
1
12
2 0
2 2
yz l s z yz l z s
x x

[ |
=
[ |
= (63)
M xy xz yz yz
s
=
[ |
1; (21)
gives
1
6
1
6
1
6
3
1
2
1
8
2 2
z l s yz z l yz s i i
x x

[ |
=
[ |
=
( )
[
\

)
|
|
|
|
|
|
= (64)
and:
M xy xz yz xz
s
=
[ |
1; (22)
gives
1
6
1
6
1
6
3
1
2
1
8
2 2
z l s xz z l xz s i i
x x

[ |
=
[ |
=
( )
[
\

)
|
|
|
|
|
|
= (65)
M xy xz yz xz xy xz yz xz
s
= +
[ |
0
1
2
; (23)
gives
1
12
2
1
2 2
2 0
2 2
xz l s z xz l z s
y y

[ |
=
[ |
= (66)
M xy xz yz xz
s
=
[ |
1; (24)
gives
1
6
1
6
1
6
3
2
1
8
2 2
z l s xz z l xz s i
i
y y

[ |
=
[ |
=
( )
[
\

)
|
|
|
|
|
|
= (67)
For M
s
= 0 of
5
B
1
mixing with
5
E

(only l
x
s
x
and l
y
s
y
):
M xy xz yz z xy xz yz z xy xz yz z xy xz yz z xy xz yz z xy xz yz z
s
= + + + + +
[ |
0
1
6
2 2 2 2 2 2
; (11)
For
5
E:
M xy xz x y z
s
=
[ |
2
2 2 2
; (25)
gives 0 (68)
M xy xz x y z xy xz x y z xy xz x y z xy xz x y z
s
= + + +
[ |
1
1
2
2 2 2 2 2 2 2 2 2 2 2 2
; (26)
gives
1
2 6
3
1
2 6
3
1
2 6
3
1
2 2
3
8
2 2 2 2
yz l s x y yz l x y s i
i
x x

[ |
=
[ |
= ( )
[
\

)
|
|
|
|
|
|
=

(69)
M
xy xz x y z xy xz x y z xy xz x y z
xy xz x y z xy xz x y z xy xz x y z
s
=
+ +
+ + +
|
|
|
|
|
|
|
|
0
1
6
2 2 2 2 2 2 2 2 2
2 2 2 2 2 2 2 2 2
; (27)
gives
1
6
3 3
2 2 2 2
x y l s yz x y l s yz +
[ |
= +
[ |
=
1
6
3 3 0
2 2 2 2
x y l yz s x y l yz s
x x x x
(70)
M xy xz x y z xy xz x y z xy xz x y z xy xz x y z
s
= + + +
[ |
1
1
2
2 2 2 2 2 2 2 2 2 2 2 2
; (28)
gives
1
2 6
3
1
2 6
3
1
2 6
3
1
2 2
3
8
2 2 2 2
yz l s x y yz l x y s i
i
x x

[ |
=
[ |
= ( )
[
\

)
|
|
|
|
|
|
=

(71)
M xy xz x y z
s
=
[ |
2
2 2 2
; (29)
gives 0 (72)
and, M
s
= 0 of
5
B
1
:
M xy xz yz z xy xz yz z xy xz yz z xy xz yz z xy xz yz z xy xz yz z
s
= + + + + +
[ |
0
1
6
2 2 2 2 2 2
; (11)
with
5
E:
M xy yz x y z
s
=
[ |
2
2 2 2
; (30)
gives 0 (73)
M xy yz x y z xy yz x y z xy yz x y z xy yz x y z
s
= + + +
[ |
1
1
2
2 2 2 2 2 2 2 2 2 2 2 2
; (31)
gives
1
2 6
3
1
2 6
3
1
2 6
3
2
1
2
3
8
2 2 2 2
xz l s x y xz l x y s i
i
y y

[ |
=
[ |
= ( )
[
\

)
|
|
|
|
|
|
= (74)
M
xy yz x y z xy yz x y z xy yz x y z
xy yz x y z xy yz x y z xy yz x y z
s
=
+ +
+ + +
|
|
|
|
|
|
|
|
0
1
6
2 2 2 2 2 2 2 2 2
2 2 2 2 2 2 2 2 2
; (32)
gives 0 (75)
M xy yz x y z xy yz x y z xy yz x y z xy yz x y z
s
= + + +
[ |
1
1
2
2 2 2 2 2 2 2 2 2 2 2 2
; (33)
gives
1
2 6
3
1
2 6
3
1
2 6
3
2
1
2
3
8
2 2 2 2
xz l s x y xz l x y s i
i
y y

[ |
=
[ |
= ( )

[
\

)
|
|
|
|
|
|
= (76)
M xy yz x y z
s
=
[ |
2
2 2 2
; (34)
gives 0 (77)
The net energy change of M
s
= 0 of
5
B
1
is:
E(M
s
= 0 of
5
B
1
) =
( )

[
\
|

)
j

[
\
|

)
j
+
[
\
|

)
j
+
[
\
|

)
j

[
\
|
|
|
|

)
j
j
j
j

2
2
5
2
5
1
2
2 2
3 5
1
0
2
1
8
1
8
1
8
1
8
E B E B
i i
E E E B ( ) ( ) ( ) ( )

[
\
|

)
j
[
\
|

)
j
+
[
\
|

)
j
+
[
\
|

)
j

[
\
|
|
|
|

)
j
j
j
j

2
2 2
3 5
1
2
2
3
8 2
3
8
1
2
3
8
1
2
3
8
i i
E E E B ( ) ( )
=

|
|
|
|
|
|
|
|

2
5
2
5
1
3 5
1
3 5
1
0
1
2
3
8
E B E B E E E B E E E B ( ) ( ) ( ) ( ) ( ) ( )
(78)
The energy difference between the of M
s
= 0 of
5
B
1
and M
s
= 1 of
5
B
1
is D:
E(M
s
= 1 of
5
B
1
) - E(M
s
= 0 of
5
B
1
)=
D
E B E B E E E B E E E B
E B E B E E E B E E E B
=

|
|
|
|
|
|
|
|

|
|
|
|
|
|
|
|

2
5
2
5
1
3 5
1
5 5
1
2
5
2
5
1
3 5
1
3 5
1
1
4
6
8
5
16
0
1
2
3
8
( ) ( ) ( ) ( ) ( ) ( )
( ) ( ) ( ) ( ) ( ) ( )
=
+

+
+

+
+

|
|
|
|
|
|
|
|
=

+
+

2
5
2
5
1
3 5
1
3 5
1
2
5
2
5
1
3 5
1
3 5
1
1
4
0
6
8
1
2
5
16
3
8
1
4
1
4
1
16
E B E B E E E B E E E B E B E B E E E B E E E B ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ))
|
|
|
|
|
|
|
|
=

|
|
|
|
|
|

2
5
2
5
1
3 5
1
3 5
1
4 4 1
E B E B E E E B E E E B ( ) ( ) ( ) ( ) ( ) ( )
(79)
Using the notation from the figure on page 1, we get,
D =

+

|
|
|
|
|
|

2
3 1
4 4 1

(80)
which is identical to equation 1.
Indeed, this is a cumbersome calculation, but it shows the paramount importance of the ligand
field contribution in second order to zfs. Moreover, when there are paramagnetic ligands, there are other
important terms to consider: contributions due to charge transfer and excited state exchange. For obvious
reasons, the latter term is called the exchange contribution, D
ex
, which results in a third-order correction
that contributes to the zfs,
D J e g
g l s e
E
J e g
g l s e
E
ex
M PL M
M M
M
PL M RL
RL RL
PL
= ( )

+ ( )



2
2
2
2
2
2
(81)
where J(e
M
g
PL
) is the exchange term of the metal excited state(s) with the ground state of the
paramagnetic ligand, and J(e
PL
g
M
) is the exchange term of the metal ground state with the excited state(s)
of the paramagnetic ligand. As can be seen, this term is directly proportional to the excited state exchange
parameter, J
ex
. In addition, unless the paramagnetic ligand has heavy atoms, the second term in (81) can
be ignored. As such, the D
ex
contribution is proportional to the single-ion contribution (given by eqn. 80)
times J(e
M
g
PL
)/E
M
.
References
1) Christou, G.; Gatteschi, D.; Hendrickson, D. N.; Sessoli, R. MRS Bulletin 2000, 66-71.
2) Krzystek, J.; Telser, J.; Pardi, L. A.; Goldberg, D. P.; Hoffman, B. M.; Brunel, L.-C. Inorg. Chem.
1999, 38, 6121-6129.