,

,
. ,
, .
,
, ..

V, .

Rh(3) ,
V.

nlm = Rnl (r )Ylm ( , ) ,
Rnl (r ) ,
, Ylm ( , ) = Plm (cos )im ,
. l
2l+1, s(l=0), p(l=2), d(l=3),
f(l=3) .. Dg(0) , Du(1) , Dg(2) , Du(3) ..
Rh(3)(3),
1. Ylm ( , )
l = 0,1,2,3 2.

1. (3) Rh(3)

Rh(3) E C(,x,y,z) i S(-,x,y.z)

Dg(0) s,
1 1 1 1 1
x2+y2+z2
Dg(1) 3 1 + 2 cos 3 1 2 cos -1 ( Rx , R y , Rz )
Dg(2) 5 1 + 2 cos + 2 cos 2 5 1 2 cos + 2 cos 2 1 AO d

j j
1 + 2 cos l 1 + (1)l cos l ( 1)
l
Dg( j ) 2 j +1 2 j +1
l =1 l =1
(0)
D u 1 1 -1 -1 -1
(x,y,z),
Du(1) 3 1 + 2 cos -3 1 + 2 cos 1
AO p
D (2)
u 5 1 + 2 cos + 2 cos 2 -5 1 + 2 cos 2 cos 2 -1
(3)
D u 7 f

j j
1 + 2 cos l 1 (1)l 2 cos l ( 1)
l
D ( j)
u
2 j +1 (2 j + 1)
l =1 l =1

1
 2. Ylm ( , )
, .

s 1 1
Y00 =
4 4
p 3 x iy 3
Y11 = sin e i
8 r 8
3 z 3
Y11 = cos
8 r 4
3 x + iy 3
Y11 = sin ei
8 r 8
d 5 3 ( x iy ) 2 5 3 2 i 2
Y2 2 = sin e
4 8 r 2 4 8
5 3 z ( x iy ) 5 3
Y21 = cos 2 e i
4 8
4 2 r2
5 1 3z 2 r 2 5 1
Y20 = (3cos 2 1)
4 4
4 4 r2
5 3
5 3 z ( x + iy ) cos 2 ei
Y21 = 4 2
4 2 r2
5 3 2 i 2
5 3 ( x + iy ) 2 sin e
Y2 2 = 4 8
4 8 r2

f 7 5 ( x iy )3
Y33 =
4 16 r 3
7 15 z ( x iy ) 2
Y3 2 =
4 8 r3
7 3 ( x iy )(5 z 2 r 2 )
Y31 =
4 16 r3
7 1 z (5 z 3r )
2 2
Y30 =
4 4 r3
7 3 ( x + iy )(5 z 2 r 2 )
Y31 =
4 16 r3
7 15 z ( x + iy )
2
Y32 =
4 8 r3
7 5 ( x + iy )3
Y33 =
4 16 r 3

2

d f .
Ho, , ,

H = Ho + V,
V ,
Ho. H
V. d:
d1. , Ho
o d (l=2),
Dg(2) Rh(3) (.
1). V Ho,
H Rh(3)
Dg(2) .
, d-
( Oh).
- Ti ( H 2 O ) 6+3 .
Dg(2)
Oh.:

3C2
Oh E 8C3 6C2 6C4 i 6S4 8S6 3h 6d
=(C4)2
A1g 1 1 1 1 1 1 1 1 1 1
A2g 1 1 -1 -1 1 1 -1 1 1 -1
Eg 2 -1 0 0 2 2 0 -1 2 0
T1g 3 0 -1 1 -1 3 1 0 -1 -1
T2g 3 0 1 -1 -1 3 -1 0 -1 1
A1u 1 1 1 1 1 -1 -1 -1 -1 -1
A2u 1 1 -1 -1 1 -1 1 -1 -1 1
Eu 2 -1 0 0 2 -2 0 1 -2 0
T1u 3 0 -1 1 -1 -3 -1 0 1 1
T2u 3 0 1 -1 -1 -3 1 0 1 -1
( Dg(2) ) 5 -1 1 -1 1 5 -1 -1 1 1
Oh
Dg(2)
1
mj =
N

g

g (g ) (g) .

1
meg = (5 2 1 + (1) (1) 8 + 1 0 6 + (1) 0 6 + 5 2 1 +
48 ,
(1) (1) 8 + 1 2 3 + 1 0 6) = 1
1
mT2 g = (15 + 0 + 6 + 6 3 + 15 + 6 + 0 3 + 6) = 1
48
3
 mg .
, Dg(2) Oh
Eg T2g,
( Dg(3) ) = (d ) = Eg T2 g .
H
Eg T2g, H
(Eg) (2g).
, ,
( Eg ) = 0 + ( Eg ) V ( Eg )
(T2 g ) = 0 + (T2 g ) V (T2 g ) ,
( E g ) (T2 g ) .
,
d
Pj = j ( g ) g .
N g
T2g :
1
0 (T2 g ) = (Y22 Y2 1 ) , + = Y21 = Y21 ,
2
Eg

1
a ( Eg ) = Y20 b ( Eg ) = (Y22 + Y21 ) .
2
,
Eg :
5 3 2 1 5
x2 y 2 = R(r ) ( x y 2 ) z 2 = R(r ) (3z 2 r 2 ) ,
4 4 2 4
T2g :
1
xy = (Y22 Y2 2 ) = NR(r ) xy
i 2
1
xz = (Y21 Y21 ) = NR(r ) xz
2
1
yz = (Y21 + Y21 ) = NR(r ) yz .
2
, Eg
, .. , T2g
.
, ,
( Eg ) V ( Eg ) 0 , (T2 g ) V (T2 g ) 0 , ( E g )
(T2 g ) d- V
10Dq, Dq>0.
( Eg ) V ( Eg ) (T2 g ) V (T2 g ) = 10 Dq .
, 5E
5 E0 = 5 0 + 2 ( E g ) V ( Eg ) + 3 (T2 g ) V (T2 g ) .
.
( Eg ) = E0 + 6 Dq ,

4
 (T2 g ) = E0 4 Dq .
:

d V
E dn ,
(eg ) k (t2 g )l , k + l=n, E = nEo+k6Dq-l4Dq.
d (n=2) ,
:

e g eg 2o+12Dq
eg t 2 g 2 o +2Dq
t2 g t2 g 2 o -8Dq

. ,
eg eg ( Eg ) ( Eg ) .
:
E g E g = A1g A2 g Eg ,
E g T2 g = T1g T2 g ,
T2 g T2 g = A1 g E g T1g T2 g .

, :

5
 .
V ( Td).
h.
2,
.
,
.
.

.1. O Oh. Oh O
.