3

(Crystal Field Theory)

(CFT) 1928 (Bethe)

K (ionic crystal) KCl
(degeneracy)

1931 (Garrick)


(crystal field)

(purely electrostatic interaction) 1935 (Van Vleck)

(crystal field splittings)

(split)

x y z ( 2)

78
1. 1 s-
s- s-
s- a1g (a
: g = gerade = even) 3.1
z

3.1 s-
: (Kettle, 1969 : 58)
2. 1 p- p-
3.2 p ( 3.2)
2 p-
p- p- p-

(triple degeneracy)
t1u ( u = ungerade = odd : t 3 )
z

z
x

px

pz

py

3.2 p-
: (Kettle, 1969 : 59)

79
3. 1 d-
d- 5 2
(lobe)
1 x y z 3 dxy
dyz dxz 3.3 x
y
z
x 3
(interchange)
3
t2g
d-
z

z
z

y
dyz

y
dxy

dxz

3.3 t2g
: (Kettle, 1969 : 59)
2 x y z 2 d

x2 y2

d z2 3.4
2 t2g-
3.4
(double degeneracy) eg (e
2 )

80
z

d z2

x2 y2

3.4 eg-
: (Kettle, 1969 : 60)
x

x d

x2 y2

d z2

t2g-
d x2 d 2 2 - d z2 d 2 2 -
y z

x y

3.5
x

d x2

y 2 z2

3.5 d

y 2 z2

d x2 -

: (Kettle, 1969 : 60)

d- d- 5
eg- t2g- 3.6
t2g- eg-

(absolute displacement)

81
eg t2g-

(bary center) 3.6

d z2 d

x2 y2

dxy dyz dxz

d z2 d

x2 y2

dxy dyz dxz

3.6 d-

: (Kettle, 1969 : 62)

4. 1 f-
7 f-
f- 3

82
1
fxyz- a2u 3.7
2 3
f 2 2
f 2 2 f 2 2 - t2u
x (y - z )

y (z - x )

z (x - y )

3.7
3 3
f x3 f y3 f z3 - t1u 3.7
z

y
fxyz

f z3 (f x3 and fy3 )

y
z (x 2- y 2 )

x (y 2- z 2 )

y (z 2- x 2 )

3.7 f-
: (Kettle, 1969 : 61)
f-
3 3.8 d-
( 3.6 ) 3.8
7
f- 3.8

83
f z3 f x 3 f y 3
f z(x2 y2 ) fx(y 2

2 f 2 2
z ) y(z x )

fxyz

f z3 f x 3 f y 3

f z(x2

2 f 2 2 f 2 2
y ) x(y z ) y(z x )

fxyz

3.8 f-

: (Kettle, 1969 : 62)

(crystal field effects in

octahedral complex)

6 (
) x y
z 3.9

84
z

x
y

3.9
: (Huheey, Keiter & Keiter, 1993 : 397)
1
3d 4s 4p-
3d- d-
d-
1 d-
5
3.10 1
2


(isotropic field) 3.10
2 d- 5

3 x y z
d- 5
eg-
t2g-
3.10 3

85
1

3
L
L

L
M
L

L
L
z
y

d z2 d x2

3/5o
x

Barycentre

eg

2/5o

dxy dxz dyz

t2g

d z2 d x2 y2

dxy dxz dyz

3.10 d-
: (Jones, 2001 : 99)
3 3.10 eg t2g-
(crystal field splitting energies) o
(o = octahedral) 10 Dq ( 10 1
D q
(electrostatic model) o
o ()

t2g-
2/5o 4Dq eg- 3/5o 6 Dq

86

3(2/5o)

=
=

2(3/5o)

d- 3



()

()

(spectroscopy)
(o)
d- (d1) Ti (H 2O)6 3 Ti3
1 3d- t2g-
eg-
t2g

eg- ( ) 3.11

eg-

t2g-

3.11 d- Ti3

87
t2g-
eg- Ti (H 2O)6 3
3.12

log

1.0
0.5
0

10000

15000

20000

25000

/cm 1

3.12 Ti (H 2O)6 3
: (Housecroft & Sharpe, 2001 : 456)
Ti (H 2O)6 3
(max) 493 nm (wave number : ) 20300 cm-1
243 kJ mol-1
(o) Ti (H 2O)6 3

Ti (H 2O)6 3
493 nm

88
E (o)

o
h

=
=
=

h
c/ ( = )
h c/

(Plancks constant)
= 6.626 10-34 J.s
= 493 nm
= 2.998 108 m s-1

(6.62610-34 J.s) (2.998108) ms-1/

(493 nm) (110-9 m nm-1)

4.029 10-19 J

Ti3+ Ti (H 2O)6 3
1
o = (4.029 10-19 J ion-1) (6.02 1023ion mol-1) (10-3 kJ J-1)
o = 242.54 kJ mol-1
(o) Ti3+ Ti (H 2O)6 3
242.54 kJ mol-1

( 3.12) 20300 cm-1

h c/
o =

=
1/
o =
hc
cm-1
o = (6.626 10-34 J.s) (2.998 108 m s-1) (20300 cm-1
102 cm m-1)
o = 4.033 10-19 J

89
o = (4.033 10-19 J ion-1)(6.02 1023 ion mol-1)(10-3kJ J-1)
o = 242.78 kJ mol-1
Ti3+ Ti (H 2O)6 3 = 242.78 kJ mol-1
o

hc

o
o

Cr (H 2O)6 2 o = 14,100 cm-1

Cr (H 2O)6 3 o = 17,400 cm-1

=
=
=

C/
1/
C

20,000 cm-1 20,000 cm-1

1.
V4
Cl VCl4
VCl6 2

VCl4

7900 cm-1

VCl6 2

15,400 cm-1

t =
o =

90
2.

Cr (H 2O)6 2

14,100 cm-1

Cr (H 2O)6 3

17,400 cm-1

Fe (CN)6 4

33,800 cm-1

Fe (CN)6 3

35,000 cm-1

3.

(Jones, 2001: 111)

Mn 2 Ni2 Co2 Fe2 V2 Fe3 Cr 3 V3
Co3 Mn 4 Rh 3 Pd 4 Ir 3 Pt 4

Fe (H 2O)6 3 o

14,000 cm-1

Co (H 2O)6 3 o

20,760 cm-1

Rh (H 2O)6 3 o

27,200 cm-1

H2O o


Fe2 Fe3 o Co3 1
Rh 3 Ir 3 2 3 Co Rh
Ir 8B Co3

91
Rh 3 Ir 3 3 NH3
3.13

o / cm-1

42000
32000
24000

3+

Co Rh3 Ir

3+

3.13 o M (NH 3 )6 3
M = Co3 Rh 3 Ir 3
: (Housecroft & Sharpe, 2001 : 457)
4. 3
(strong field ligand) (intermidiat field ligand)
(weak field ligand)

(Jones, 2001 : 112)

weak field ligand
I Br S2- SCN Cl N 3 F (NH2)2-C = 0
OH O2C CO22- O2- H2O NCS NC5H5(py) NH3
2,2-N C5H5C5H5N(bpy) NO2 CH3 CN CO
strong field ligand

92
(spectrochemical
series)

Ru (H 2O)6 2

19,800 cm-1

Ru (CN)6 4

33,800 cm-1

Rh (H 2O)6 3

27,200 cm-1

Rh (NH3 )6 3

34,100 cm-1

Ru2+ H2O
CN o Ru (CN)6 4 Ru (H 2O)6 2
CN H2O Rh(H 2O)6 3

Rh(NH3 )6 3 NH3 H2O

1. H2O OH OH

OH H2O
2. NH3 H2O H2O
(dipole moment) NH3 H2O NH3
H2O
NH3
3. bpy H2O bpy
H2O

( 4)

93

d- (distribution of d-electron)
d- 5
1 d-
5
d- 5 ()
t2g- eg- d-
()
(spin) ()
d1 - d10
2
1. (high spin)
(weak field complex)

(pairing energy : P
) (o P) d1- d10
3.1
2. (low spin)
(strong field complex)
(o P)
d1 - d10 3.1

94
3.1 d-

d1
o

d2

d4

d5

eg

eg

eg

eg

eg

t2g

t2g

t2g

t2g

t2g

d6
o

d3

d7

d8

d9

d10

eg

eg

eg

eg

eg

t2g

t2g

t2g

t2g

t2g

d1
o

d2

d4

d5

eg

eg

eg

eg

eg

t2g

t2g

t2g

t2g

t2g

d6
o

d3

d7

d8

d9

d10

eg

eg

eg

eg

eg

t2g

t2g

t2g

t2g

t2g

: (Miessler & Tarr, 2004 : 348)

95
3.1 d1 - d3 d8 - d10
d4-d7

(o)
Fe (CN)6 4
Fe2 d- 6 (d6)
d6 () 3.1

Fe (H 2O)6 2 d6
() 4

(Crystal Field Stabilization Energy : CFSE)

d- eg-
() t2g-


1
() d t2g-
(2/5 o)
d1 : CFSE (2/5o)
CFSE

CFSE
x y
t2g eg

96
1. CFSE
CFSE
= y(3/5) x(2/5) o
CFSE d2

CFSE

t 22g e 0g
CFSE
= O(3/5) 2(2/5) o

CFSE d2 =

-(4/5) o

2. CFSE
CFSE d6
4 e2
t 2g
g
CFSE
CFSE
= y(3/5) x(2/5) o + aP
a
CFSE
= 2(3/5) 4(2/5) o + P

CFSE d6 =

-(2/5) o+P

d6 t2g
1 ( 3.2)
d5 () t 32g e2g
( 3.2) CFSE = 0
CFSE
3.2

97
3.2 CFSE

d1

d2

d3

eg
o -(2/5)o

d4

eg

eg

-(4/5)o

-(6/5)o

t2g

d5
eg

eg
0

-(3/5)o

t2g

t2g

CFSE

t2g

t2g

d4

d5

d6

eg
o -(8/5)o +P

d7

eg
-(10/5)o +2P

t2g

eg

eg
-(9/5)o +3P CFSE

-(12/5)o +3P

t2g

t2g

t2g

d6

d7
eg

o -(2/5)o+P

d8
eg

-(4/5)o+2P

t2g

: (Jones, 2001 : 101)

d9
eg

-(6/5)o+3P

t2g

d10
eg

-(3/5)o+4P

t2g

eg
0+5P

t2g

CFSE

t2g

98
3.2 CFSE
d1- d10 d1- d3 d4 ()
CFSE
d4- d7 () d6- d10 ()
CFSE P
CFSE
5-10 % CFSE

- (Jahn-Teller
effect in octahedral complex)
2 ( 2)
- C4
eg-
d4 ()

t 32g

e1g

Cr 2 Mn 3

d7 ()

t 62g

e1g

Co2 Ni3

d9 ()

t 62g

e3g

Cu2

t2g-
t2g x y z
(detect)
Cu2 (d9)
t 62g e3g 3 eg- 2

1 (d x2 y2 )1 (d z2 )2 2 (d x2 y2 )2 (d z2 )1

99
1 d x2 y2
d z2 x y
z z 1 (shield)
4 x y 2
z z ( z)
Cu(NO2 )6 4 3.14
231.3

205.0

NO2
O 2N

NO2
Cu

205.0

O 2N
205.2

4-

205.2

NO2
NO2

231.3

3.14 Cu(NO2 )6 4 z
( Cu-N pm )
: (Jones, 2001 : 106)
2 d z2
d x2 y2 z
x y 2 z
4 x y z
( z) Cu2
z

z
3.15

100
L

L
L

L
L

L
L

L
1/2 1
1/2 1

d x2 y2 d z2

L
L

d x2 y2

d z2

dxy
2/3 2
1/3 2

dxy dxz dyz

dxz dyz

3.15
: (Jones, 2001 : 107)
t2g- eg-
d x2 y2 - eg-
d z2 eg- d x2 y2 d z2 -

1 dxy- t2g- dxz dyz-

t2g- dxy dyz-
2 3.15
CFSE 2
CFSE =
3(3/5) 6(2/5) o = -3/5o
CFSE

-3/5o + (22/3) 2-(41/3) 2

+(1/21) (21/2) 1

-3/5o 1/2 1

101
CFSE

z
z 3.16
z

z
y

d z2

d x2 y2
1

1/2 1
1/2 1 o
d z2
dxy

eg

1/2 1

d x2 y2 d z2

1/2 1

d x2 y2

dxz dyz

2/3 1

t2g

1/3 2

1/3 2
dxz dyz

dxy dyz dxz

2/3 2

dxy

3.16
z z
: (Huheey, Keiter & Keiter, 1993 : 450)

102
z z
3.16 z z
z 3.16
o o 1 2

z z
4
z 3.17

L
L
M
L

L
L

L
L

L
d x2 y2

E
d x2 y2 d 2
z

dxy

d z2
dxy dxz dyz

dxz dyz

3.17 d8

: (Jones, 2001 : 109)

103
3.17
d8 t 62g e2g ()
6 d x2 y2 1 4 x y
d z2 1 z 2
d x2 y2 d z2 () CN

Ni(CN)4 2 d x2y2 d z2 -
z
3.17
Rh Ir Pd 2 Pt 2 Au3 d8
d x2 y2 d z2
2 3 8
3.17

d-
2
1 t2- 3 dxy dyz dxz
2 e- 2 d x2y2 d z2

3.18

1
(4 ) 2 (4 3
) d-

104
+z

-y
-x
+x
+y
-z
3.18
: (Huheey, Keiter & keiter, 1993 : 402)

3.19 4
d- t2 e
z
l/2
1/2

l/2

y
l l

x
l
dxy

dyz

dxz

l 2/2

l 2/2

d x2 y2

d z2

3.19 d-

: (Rodgers, 1994 : 66)

105
l 4
d- t2 l/2 0.5 l ( 3.19)
d- e 2 .l/2 0.7 l
t2- e-
3.20
t2
2/5t

Bary center

E
3/5t

d-
e

3.20 d-

t2 e- t (t = tetrahedral)
t2- 2/5 t e- 3/5 t
e- t2-
(point charge model)

t o

3.21

4/9 o

1/2 o

106

eg

t2
E

Bary center

d-
e
t2g

t = 4/9 o

3.21 o t

t o

Co(NH3 )4 2 ()

5,900 cm-1

Co(NH3 )6 2 () 0

10,200 cm-1

t c (c = cubic) c
t c 3.22

107

L
L
M

L
M
L

L
L

L
L

M
L

z
dxy dxz dyz

y
x

dxy dxz dyz

c= (8/9)o

t2

t= (4/9)o

e
d z2 d x2 y2

d z2 d x 2 y 2

3.22 c t o
: (Jones, 2001 : 108)

3.22 c 2 t

c
o
c

8/9 o

4/9 o

108
d-
d-
3.3

Emery/o

3.3 d-
1.2
1.1
1.0
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
-0.1
-0.2
-0.3
-0.4
-0.5
-0.6
-0.7

d x2 y2

d x2 y2
d z2

d z2 d x 2 y 2
d z2
dxy d x2 y2

dxy

dxz

dxy

dxy

dyz
dyz

dxy dxz dyz

dxz

Square
pyramid

Octahedral

Pentagonal
bipyramid

dxz

dyz

Barycenter

d z2

dxy d x2 y2
d z2
dxz

dxz

dyz

d x2 y2

d z2

dyz

Square
planar

Trigonal
bipyramid

Square
antiprism

: (Housecroft and Sharpe, 2001 : 460)

3.3 d-
o
dxy dyz dxz-
= -0.4o (
2/5o ) d x2 y2 d z2 = + 0.6 o
(+3/5o) d- 3.3

dxz dyz

-0.514o

d z2

-0.428o

dxy

+0.228o

d x2 y2

+1.228o

109

( 7)

( 6)

d-
5

(CFSE)

110

1.

1.2 d3
1.1 d1
1.3 d5

1.4

d7

1.5 d9
2.
H2O Cl acac NH3
2.1 Cr 2
2.2 Co3
2.3 Ni2
2.4 V2
3.

3.1 CO F
3.2 CN OH
3.3 en H2O
3.4 NH3 I
4. Ni Cl4 2 Ni(CN)4 2

4.1 Ni2+
4.2
5. d x2 y2 dxy

6. d-

6.1 CrF6 3
6.2 V(H2O)6 3
6.3 Fe(CN)6 3 6.4 Cu(en)3 2

111
7. Ti(NCS) 6 3 544 nm
kJ mol-1
7.1 NCS H2O
7.2 Ti(NCS)6 3
8. Cr(H 2O)6 3 Cr(CN)6 3

9.

10. o
10.1 Cr F6 3 Cr F 6 4
10.2 Fe (CN)6 4 Fe (CN)6 3
10.3 Mn F6 2 Re F6 2
10.4 Ni (H 2O)6 2 Ni (CN)6 4