) (2010

" , ".

1.1

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

1.2

. . . . . . . . . . . . . . . . . . . . . . . . . . .

. . . . . . . . . . . . . . . . . . . . . . .

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

11

1.2.1
1.3
2

12

2.1

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

12

2.2

. . . . . . . . . . . . .

12

2.3

. . . . . . . . . . . . . . . . . . . . . . . . . . . .

13

2.4

. . . . . . . . . . . . . . . . . . . . . . . . . . . . .

13

2.4.1

14 . . . . . . . . . . . . . . . . . . . CG

2.4.2

15 . . . . . . . . . . . . . . . . . . . . . . . . . CG

2.4.3

. . . . . . . . . . . . . . . . . . . . . CG

17

2.5

. . . . . . . . . . . . . . . . . . . . . . . . . . .

18

2.6

, . . . . . . . . . . . . . . . . . . .

20

2.7

1
2

2.6.1

20 . . . . . . . . . . . . . . . .

2.6.2

)( )( 24 . . . . . . .

2.6.3

27 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

2.6.4

28 . . . . . . . . . . . . . . . . . . . . . . . . .

2.6.5

? 29 . . . . . . . . . . . . . . . . . . . .

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2

32

3.1

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

33

3.2

. . . . . . . . . . . . . . . . . . . .

33

3.3

3.2.1

35 . . . . . . . . . . . . . . . . . . . .

3.2.2

35 . . . . . . . . . . . . . . . . . . . . . .

3.2.3

: 38 . . . . . . . . . . . . . . . . .
3.2.3.1

. . . . . . . . . . . . . . . . . . . .

39

3.2.3.2

. . . . . . . . . . . . . . . .

40

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

41

3.3.1
3.4
4

: 43 . . . . . . .

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

44
46

4.1

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

46

4.2

. . . . . . . . . . . . . . . . . . . . . .

46

4.2.1

47 . . . . . . . . . . . . . . . . . . . . . .

4.2.2

49 . . . . . . . . . . . . . . . .

4.3

. . . . . . . . . . . . . . . . . . . . . . Bloch

49

4.4

. . . . . . . . . . . . . .

50

4.4.1
4.5
5

33

51 . . . P auli

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

5.1

5.2

54
56

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

56

5.1.1

56 . . . . . . . . . . . . . . .

5.1.2

59 . . . . . . . . . . . . .
5.1.2.1

. . . . . . . . . . . . . .

59

5.1.2.2

. . . . . . . . . . . . . . . . . . . . .

61

. . . . . . . . . . . . . . . . . . . .

62

5.2.1

64 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3

5.3

5.2.1.1

' . . . . . . . . . . . . . . . . . . .

64

5.2.1.2

. . . . . . . . . . . . . . . . . . .

64

5.2.2

65 . . . . . . . . . . . . . . . . . . . . . . . . . . . Hartree

5.2.3

66 . . . . . . . . . . . . . . . . . . . . . . Hartree F ock

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.3.1

67 . . . . . . . . . . . .

5.3.2

68 . . . . . . . . . . . . . . . . . . .
5.3.2.1

68

5.4

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Hund

71

5.5

. . . . . . . . . . .

74

5.6

Zeeman . . . . . . . . . . . . . . . .

77

5.6.1
5.7
6

67

78 . . . . . . . . . . . . . . . . . . . . . . Land
e

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

79
80

6.1

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

80

6.2

. . . . . . . . . . . . . . . . . . . . . . Born Oppenheimer

81

6.3

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . H2+

82

6.4

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . H2

85

6.4.1

85 . . . . . . . . . . . . . . . . . . . . . .

6.4.2

85 . . . . . . . . . . . . . . . . . . . . . Heitler London

6.5

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

87

6.6

. . . . . . . . . . . . . . . . . . . . . . . . . . V an der W aals

88

6.7

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

90
92

7.1

. . . . . . . . . . . . . . . . . . . . . . . . . . . .

92

7.2

. . . . . . . . . . . . . . . . . . . . . . . .

93

7.3

. . . . . . . . . . . . . . . . . . . . . . . . . . . F ermi

94

7.4

. . . . . . . . . . . . . . . . . . . . . . . . . . . .

97

7.5

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

97

8.1

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
8.1.1

8.2

99

) ( 99 . . . . .
8.1.1.1

100 . . . . . . . . . . . . . . . . . . . . . . . .

8.1.1.2

100 . . . . . . . . . . . . . . . . . . . . . . . .

8.1.2

101 . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

8.1.3

101 . . . . . . . . . . . . . . . . . .

8.1.4

102 . . . . . . . . . . . . . . . . . . .

103 . . . . . . . . . . . . . . . . . .
8.2.1

) A(r, t 104 . . . . . . . . . . . . . . .
8.2.1.1

8.3

99

105 . . . . . . . . . . . . . . . . . . . . .

106 . . . . . . . . . . . . . . . . . . .
8.3.1

106 . . . . . . . . . . . . . . . . . . . . .

8.3.2

108 . . . . . . . . . . . . . . . . . . . . . . .

8.3.3

109 . . . . . . . .

8.3.4

109 . . . . . . . . . . . . . . . . . .
8.3.4.1

: Zeeman
111 . . . . . . . . . . . . . . . . . . . . . . . . .

8.4
9

8.3.5

113 . . . . . . . . . . . . . . . . . . . . . . . .

8.3.6

116 . . . . . . . . . . . . . . . . . . . . . .

118 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
120

9.1

120 . . . . . . . . . . . . . . . . . . . . . . . . . . . .

9.2

121 . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

9.3

123 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

9.4

125 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Born

9.5

126 . . . . . . . . . . . . . . . . . . . . . . . . . . .

9.6

128 . . . . . . . . . . . . . . . F ermi

9.7

129 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5

 10

131

10.1 131 . . . . . . . . . . . . . . . . . . . . . . . . . .
10.2 133 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
10.3 134 . . . . . . . . . . . . . . . . . . .
10.4 136 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

1.1

:
. .

1.2

,1 B:
H = B
, ":
~e
S
2me c

= ge

ge g S ,2 ,
B = e~/2me c .Bohr )
:(ge = 2
H = B B
,z
.B = B0 z :
H = B z B0
, :
B B0 | i

= H| i

B B0 | i

= H| i

 |(t = 0)i = a| i + b| i ,t = 0
!
a
b
" :
i

|(t)i = e ~ Ht |(t = 0)i

~ L 2B B0 /:
!
i
ae 2 L t
= |(t)i
i
be 2 L t
y ,x z |i :t
!
!
 1 0

2i L t
ae
i
i

= h(t)|z |(t)i
a e2 L b e 2 L
i
0 1
be 2 L t
!

ae 2 L t
i

be 2 L t

2i L t

= |a|2 |b|2

i
= h(t)|x |(t)i
a e 2 L t

b e

ae 2 L t

be 2 L t

)2|ab|cos (L t +


i
i
= h(t)|y |(t)i
a e 2 L t b e 2 L t
)2|ab|sin (L t +

hz i , hx i hy i
.L hi z ) L
.(1.1 .

1.2.1

) ,B1 = B1 cos(t
, , x ,x
.B1  B0 :
= B B

))= B (z B0 + x B1 cos(t
!

B0

)B1 cos(t

B1 cos(t) B0

= B

|(t)i:
!

a
b

a
b

B0

)B1 cos(t

B1 cos(t) B0
8

!
= H

= B

a
b

d
dt

~i

 :1.1

~ 1 B B1 / :
1
L a + 1 cos(t)b
2
1
1 cos(t)a L b
2

= ia
= ib

L
:
i

= a(t)e 2 L t

)A(t

= b(t)e 2 L t

)B(t

)(1.1

)(1.2

1 cos(t) BeiL t

1  i(L )t
B e
+ ei(L +)t
2
1 cos(t) AeiL t

1  i(L )t
A e
+ ei(L +)t
2

= iA
=
=

iB

,:
)(1.3

|L |  L

, B1 ,hx i hx i
) ( , B1 . , ,
9

 . ,
. ,1.3
|L |  L +
1.1 ,1.2 .
"" ,
, . 1:
1 i(L )t
Be
2
1 i(L )t
Ae
2

iA

iB

|(t = 0)i = | i
:
0

)A(0

)B(0

, = L:


1 t
isin
2


1 t
cos
2

)A(t

)B(t

, ,t1 = /1 )
(
!
= | i

= )i
1

(|

! ,t2 = /21

i
1

, .xy
B1 t1 " ," ,t2
" ." 2 , ,B1
L
1 ? , , ...

10

 . ,
) M RI
) L(proton) 240M Hz
L(electron) 180GHz 6( ,
(.

1.3

.1 , ,
.
.2 , , .
, ,
: , ,'.
.3 ) (
) .( 2
.4 , , ,
.
.5 , .
.M RI

11

2.1

1 L2 Lz ,
L2 .Lz ,|lmi:
~2 l(l + 1)|lmi

= L2 |lmi

~m|lmi

= Lz |lmi

, |lmi L2 ) ~2 l(l + 1 Lz
.~m , .
, ,
) (L ) .(S "
) .(J ,
, .J

2.2

) ( .
, .
|l1 m1 i .|l2 m2 i
, . ,
" . ,
.
) ( ,
.
12


.
|l1 m1 i |l2 m2 i .|l1 l2 m1 m2 i ,
. ,
l2 m2 l1 m1 . ,
l1 , m1 l2 , m2.
? Lz L1z
L .L1 L2z .L2
.
:L1z
L1z |l1 l2 m1 m2 i = ~m1 |l1 l2 m1 m2 i
:
l1 (l1 + 1) m1 (m1 + 1)|l1 , l2 , m1 + 1, m2 i

= L1+ |l1 l2 m1 m2 i

, ,
. :
0

] [L1z , L2z

] [L21 , L22

" L22 ,L21 ,L2z ,L1z ,

|l1 l2 m1 m2 i .

2.3

. ,L2z ,L1z
.L22 ,L21 , ,
L2 = (L1 + L2 )2 .Lz = L1z + L2z
.
) L22 ,L21 ,L2 ,Lz
( . .|l1 l2 lmi

2.4

|l1 l2 m1 m2 i .|l1 l2 lmi ,

:
X
= |l1 l2 lmi
i |l1 l2 m1 m2 i
i

13

 i ) Clebsch Gordan ,(CG

. ,
, :
X
hl1 l2 m1 m2 |l1 l2 lmi |l1 l2 m1 m2 i

)(2.1

= |l1 l2 lmi

)(
hl1 l2 m1 m2 |l1 l2 lmi .hl1 l2 m1 m2 |lmi ?

2.4.1

CG

m .l , = m
l, l + 1, ..., l m m1 ,m2 l l1 ?l2
:
(L1z + L2z )|l1 l2 m1 m2 i

= Lz |l1 l2 m1 m2 i

L1z |l1 l2 m1 m2 i + L2z |l1 l2 m1 m2 i

~m1 |l1 l2 m1 m2 i + ~m2 |l1 l2 m1 m2 i

~(m1 + m2 )|l1 l2 m1 m2 i

, Lz = ~m
) .~(m1 + m2 , .m = m1 + m2
:CG m 6= m1 + m2 .hl1 l2 m1 m2 |lmi = 0
.l L1 L2
, |L1 | = l1 .|L2 | = l2
L1 + L2 = L . ,l ,
l1 ?l2 L1 L2 .
, L .l = l1 + l2 , , L1 L2
, L | .l = |l1 l2 ,
)(2.2

|l1 l2 | l l1 + l2

, , ,
, . , l1
2l1 + 1 ,m1 l2 2l2 + 1
.m2 " l1 , l2 , ) (2l1 + 1)(2l2 + 1 .
, l1 , l2 l , .2.2
,l 2l + 1 .m , l1 , l2 ,

14

 ) (:
lX
1 +l2

l+

| l=|l1 l2

lX
1 +l2

)(2l + 1

| l=|l1 l2

lX
1 +l2

| l=|l1 l2

)(l1 + l2 + |l1 l2 |)(l1 + l2 |l1 l2 | + 1

= 2
2
]+ [l1 + l2 |l1 l2 | + 1

)(l1 + l2 + |l1 l2 | + 1)(l1 + l2 |l1 l2 | + 1

(l1 + l2 + 1)2 (l1 l2 )2

1 + 2l1 + 2l2 + 4l1 l2

)(2l1 + 1)(2l2 + 1

. , CG : l > l1 + l2 | l < |l1 l2

.hl1 l2 m1 m2 |lmi = 0
= hl1 l2 m1 m2 |lmi m = m1 + m2
, 6 0
.|l1 l2 | l l1 + l2 , 1 CG m1 = l1
m2 = l l1 :
)(2.3

2.4.2

hl, l|l1 , l2 , l1 , l l1 i = hl1 , l2 , l1 , l l1 |l, li 0

CG

3
2

= l1 .l2 = 1

,l = l1 + l2 ,2.2:
1 3 5
, ,
2 2 2

=l

,|l1 , l2 , m1 , m2 i .|l, mi
m = m1 + m2 :
3
3
5 5
| , i = | , 1, , 1i
2 2
2
2

5
2

= m

3
2

= m1 .m2 = 1

L , :
r
5 5
5 5
5 3
5 5
= L | , i
( + 1) ( 1) | , i
2 2
2 2
2 2
2 2

5 3
=
5| , i
2 2
1 ?
ei . .
15

 :
5 5
3
3
L | , i = L | , 1, , 1i
2 2
2
2
3
3
(L1 + L2 ) | , 1, , 1i
2
2
r
3 3
3 3
3
1
=
( + 1) ( 1) | , 1, , 1i
2 2
2 2
2
2
p
3
3
+ 1(1 + 1) 1(1 1) | , 1, , 0i
2
2

1
3
3
3
=
3 | , 1, , 1i + 2 | , 1, , 0i
2
2
2
2
=

:
2 3
3
| , 1, , 0i
5 2
2

)(2.4

3 3
1
| , 1, , 1i +
5 2
2

5 3
=| , i
2 2

:m = 32
r
r
1
3
3 3
2 3
3 3
| , 1, , 1i +
| , 1, , 0i
)(2.5
| , i=
2 2
5 2
2
5 2
2

3 3
3
| , 1, , 0i
5 2
2

2 3
1
| , 1, , 1i
5 2
2

.2.3 L 2.4 .2.5

2.4:
!

1
3
3 3
2 3
| , 1, , 1i +
| , 1, , 0i
5 2
2
5 2
2
!
r
r
1
3
3 3
2 3
| , 1, , 1i +
| , 1, , 0i
) = (L1 + L2
5 2
2
5 2
2
r
r

1
1
3 3
2 3
= 2
| , 1, , 1i + 3
| , 1, , 0i
5 2
2
5 2
2
r
r

3 3
1
2 3
3
+ 2
| , 1, , 0i + 2
| , 1, , 1i
5 2
2
5 2
2
L

5 3
= L | , i
2 2

:
1 3
3
| , 1, , 1i
10 2
2

3 3
1
| , 1, , 0i +
5 2
2

3 3
1
| , 1, , 1i +
10 2
2

L :2.5
r
r
8 3
1
1 3
1
2 3
3
| , 1, , 1i +
| , 1, , 0i +
| , 1, , 1i
15 2
2
15 2
2
5 2
2

5 1
=| , i
2 2

3 1
| , i=
2 2

m = 12:
r
r
r
1 1
1 3
1
1 3
1
1 3
3
=| , i
| , 1, , 1i
| , 1, , 0i +
| , 1, , 1i
2 2
6 2
2
3 2
2
2 2
2
16

 CG ) :(hl1 , l2 , m1 , m2 |l, mi
3
3 5 5
h , 1, , 1| , i = 1
2
2 2 2
r
3
3
1 5 3
= h , 1, , 1| , i
2
2 2 2
5
r
3
3 5 3
2
= h , 1, , 0| , i
2
2 2 2
5
r
2
3
1 3 3
h , 1, , 1| , i =
2
2 2 2
5
r
3
3
3 3 3
= h , 1, , 0| , i
2
2 2 2
5
r
3
3
1 5 1
= h , 1, , 1| , i
2
2 2 2
10
r
1 5 1
3
3
= h , 1, , 0| , i
2
2 2 2
5
r
3
3
5 1
1
= h , 1, , 1| , i
2
2
2 2
10
. , ,
.
.
m1 ,m2 :
3 1 1 3
, , ,
2 2 2 2
1, 0, 1

m1

m2

m1 .m2 "
) .(2.1 ) (| 52 , 52 i = | 32 , 1, 32 , 1i
. L

. .m = m1 + m2
L
'.

2.4.3

CG

.CG
hl1 l2 m1 m2 |L+ |l1 l2 lmi :
.1 L+:
l(l + 1) m(m + 1)hl1 l2 m1 m2 |l1 , l2 , l, m + 1i

17

= hl1 l2 m1 m2 |L+ |l1 l2 lmi

 :2.1

3
2

= l1 .l2 = 1

.2 ) (L+ . , :
(L+ ) = L = L1 + L2
:
l1 (l1 + 1) m1 (m1 1)hl1 , l2 , m1 1, m2 |l1 l2 lmi

= hl1 l2 m1 m2 |L+ |l1 l2 lmi

l2 (l2 + 1) m2 (m2 1)hl1 , l2 , m1 , m2 1|l1 l2 lmi

:
p
)l1 (l1 + 1) m1 (m1 1
p
hl1 l2 , m1 1, m2 |l1 l2 lmi
)l(l + 1) m(m + 1
p
)l2 (l2 + 1) m2 (m2 1
p
hl1 , l2 , m1 , m2 1|l1 l2 lmi
)l(l + 1) m(m + 1

= hl1 l2 m1 m2 |l, m + 1i
+

) (
.hl1 l2 m1 m2 |L |l1 l2 lmi
, CG
.

2.5

1
2

S2 Sz
:
| i

| i

1
1
,m = + i
2
2
1
1
|s = , m = i
2
2

= |s

18

 :
}{| i, | i, | i, | i
,S22 ,S21 ,S2z ,S1z
) S22 ,S21 ,S2 ,Sz , S2 = ,
(S1 + S2 )2 .(Sz = S1z + S2z 2.2
s ) s = 0 (m = 0 ) s = 1 .(m = 1, 0, 1 ,
.~ = 1
| i

1
2

= ,m1

1
2

= ,m2:

Sz | i = S1z | i + S2z | i
1
1
| i + | i
=
2
2
= | i
, | i Sz .m = 1:
S1+ | i + S2+ | i

= S+ | i

0+0

S2 = S S+ + Sz2 + Sz:
0 + | i + | i

= S 2 | i

2| i

1(1 + 1)| i

, | i S2 .s = 1 ,
| i Sz ,m = 1 S2
.s = 1 ,s = 1 ,m = 0
.s = 0 ,m = 0 S .| i
:
S |s = 1, m = 1i
p
s(s + 1) m(m 1)|s = 1, m = 0i

2|s = 1, m = 0i

= S | i
=
=

:
S1 | i + S2 | i
r
r
1 1
1 1
1 1
1 1
( + 1) ( 1)| i +
( + 1) ( 1)| i
2 2
2 2
2 2
2 2
| i + | i
19

= S | i
=
=

:
| i + | i

= |s = 1, m = 0i

,|s = 0, m = 0i
." :
|s1 = 12 , s2 = 12 , s = 1, m = 1i = | i
)i + | i
)i | i

|( 1
2

|s1 = 12 , s2 = 12 , s = 1, m = 0i

= | i

= 1, m = 1i

= 0, m = 0i

|( 1
2

1
2, s
1
2, s

=
=

1
2 , s2
1
2 , s2

= |s1
= |s1

) (s = 1 "" ,
"" . , ,
, .
, ,
, !
,
. , ,
.EP R

2.6

,
. .

2.6.1

"
.R , , |i
?R |i ,|0 i
,R ) D(R .|0 i = D(R)|i , R
) D(R . , ) ,D(R
?R
R Ri
, Ri
" n

) n ( .
( .D ,
.
n=z
)n,
i

(.D
: ,zz, ) = e ~ Lz :
20

d
d
.Lz = i~(x dy
y dx
: Lz )
d

.Lz = i~ d ) (r, , ) (.
i

( D :
" z, ) = e ~ Lz


i
i
1 i
)1 + Lz + ( Lz )2 + ... (r, ,
= )e ~ Lz (r, ,
~
~ 2


d
1
d2
=
1+
)+ 2 2 + ... (r, ,
d 2 d
d
1 d2
= (r, , ) +
(r, , ) 2 + ...
(r, , ) +
d
2 d2
)= (r, , +
i

.
, e ~ Lz z

, Lz "" .z
Lx "" x Ly ""
.y :
,:
: n
i

(D
n, ) = e ~ Ln

)(2.6

.
, J
.L
() D .(D
)n,
J2 ?Jz
, ... j , :
)(2.7
)(2.8

hj, m0 |D(R)|j, mi
|j, mi

i
n
~ J

)(j

Dm0 m

= hj, m |e

j?
D j.
hj 0 , m0 |D|j, mi = 0 : .j 6= j 0
: .[D, J2 ] = 0 , J2
1

( , ) .(e ~ Jn
) n
.[D, J2 ] = 0 , :
J2 D|j, mi = DJ2 |j, mi
= j(j + 1)~2 D|j, mi
21

 :2.2 D .|jmi

:2.3 " "j .D

D|j, mi , J2 ,j(j + 1)~2

| hj 0 , m0 .j 0 6= j

D .|j, mi
j 2j + 1 ,m 2j + 1 2j + 1
.j .2.8 "
, j , . ,
j . ,
|j, mi D
) ,(2.2 ) .(2j + 1) (2j + 1 , ,
) .(2.3 .
: ,jN }Vj = span {|j, mi : m = j, j + 1, ..., j
.
22

 : ,Uj Vj .D : Uj Uj .|i Uj
,Uj |i .
|i = |j, ji . ,
?

= ,|i ,P
6 |j, ji

,|i = P |j, ji = P Ji P

.Ji0

Ji0

( ,Ji .Ji
,|j, mi0 = P |j, mi .|j, ji0 = |i
0 , .|i = |j, ji
.|i :

iJ n
~

D =1

,2.6 , J .L:
| 0 i = D|i
= D|j, ji



iJ n
=
1
|j, ji
~


i (J n
+ + J+ n
+ 2Jz n
) z
|j, ji
=
1
~2
:
n
= n
x i
ny

J+ |j, ji = 0

Jz |j, ji = ~j|j, ji

p
J |jji = ~ 2j|j, j 1i
:

1 p
i 2j
n+ |j, j 1i
2

| 0 i = (1 ij
nz ) |j, ji

,(1 ij
,D : Uj Uj .| 0 i Uj nz ) |j, ji Uj
.|j, j 1i Uj 2j + 1
|j, ji , ... , |j, j 1i ,|j, ji .Uj ,
,dimUj = 2j + 1 = dimVj Uj Vj .Uj = Vj
23


|i .D
|j, mi |i .D
, |i ,j
j . , j
.D , , j
.
.

2.6.2

)( )(

,
.
: R . ) V = (V1 , V2 , V3 )
, ( , ,
,V0 = RV:
)(2.9

Rij Vj

3
X

= V 0i

j=1

,i = 1, 2, 3 .R
. , ,
" " ,
.
: R , |i . ) = (V1 , V2 , V3
V
0 = RV
, ,
,V:
)(2.10

Rij h|Vj |i

3
X

= h|Vi0 |i

j=1

i = 1, 2, 3 .R
.
, .
. ,
:
L=rp
, .
,
, .
24

 : J1 , J2 , J3 :
[Ji , Jj ] = iijk ~Jk
.i, j, k = 1, 2, 3 ) .J = (J1 , J2 , J3 ,
,.J = J1 iJ2 ,
:
: ) J = (J1 , J2 , J3 . ) V = (V1 , V2 , V3

)(2.11

[Vi , Jj ] = iijk ~Vk

.i, j, k = 1, 2, 3 Vi ) V
(.

.
: J ) (.
. :
: ) J = (J1 , J2 , J3 . S
[S, Ji ] = 0
.i = 1, 2, 3
: H , ,
.
: .
: "
) ."SU (2 ,
, ,
.
: , ,
. ,
. , ,
,
.
.
: .

25

 : . R
) D(R . 2.10 :
h0 |Vi |0 i
h|D (R)Vi D(R)|i

)(2.12

= h|Vi0 |i
=

, 2.10 2.12 ,|i

:
)(2.13

Rij Vj

3
X

= )D (R)Vi D(R

j=1

, .
) (:

iJ n
~

D(R) = 1

2.13:


3
X

iJ n
Rij Vi
Vi 1
=
~
j=1
)(2.14

Rij Vi

3
X

]
[Vi , J n
~i

j=1

iJ n
~


1+

Vi +

.2 ,
n ,z
:

0
1

R=

2.14 :
V1 V2

] i~ [V1 , Jz

~V 2 + i
] [V2 , Jz

] V3 + i~ [V3 , Jz

i = 1 : V1 +

= V1 + V2
= V3

i=2:
i=3:

:
[Vi , Jj ] = iijk ~Vk
, , ,
2.6 ) (.

26

 .
: L1 L2 . J = L1 + L2 , .
:
] [L1x + L2x , L1y + L2y

] [L1x , L1y ] + [L1x , L2y ] + [L2x , L1y ] + [L2x , L2y

] [Jx , Jy

= iL1z + 0 + 0 + iL2z
= iJz
.


2.6.3

) (
. ,
. , 2.9
:
)(2.15

Rii0 Rjj 0 Rkk0 Ti0 j 0 k0 ...

XXX
k0

j0

Tijk...

i0

Tijk... ,T
.
,U V :
)(2.16

Tij Ui Vj

.2 9 " "
.2.15 , 2.15 , .
.2.16 :

 
 

UV
Ui V j Uj V i
Ui Vj + Uj Vi
UV
= Ui Vj
ij +
+

ij
)(2.17
3
2
2
3
,
. , .
, ) ,
,(1 ) 3 , ,(3
) traceless tensor .(5
2.16 , .
:
.
27

2.6.4

, ) (?
,2.17 ?
, 3 ,1 5 , ,
. 2.6.1
|j, mi !j
} {|j, mi : m = j, j + 1, .., j 2j + 1 .
)""
,|j, mi .(Ylm
,k 2k + 1
: n
o
)(k
)(k
,T = Tq : q = k, k + 1, ..., k
|j, mi j = k :m = q
)(k

)Dq0 q Tq(k

= DTq(k) D

q0

)(k
Dq0 q |k, qi

= D|k, qi

q0
)(k

Dq0 q .2.7

)(k

Tq "

) ,"T(k , " ".

,
. ,
.
: J . k 2k + 1

o
n
)(k
= Tq : q = k, k + 1, ..., k

)(k

T:
)(k

)(k

] [Jz , Tq

~qTq
p
)(k
= ~ k(k + 1) q(q 1)Tq1

)(k
] [J , Tq

: V , V1 , V2 , V3
) 12 (V1 + iV2

)(1

V3

)(1

1 (V1
2

)(2.18

) iV2

V1
V0

)(1
V1

) V(1 .1 , J
.1
28

 : |l, mi
:
4
)Ykq (,
2k + 1

2.6.5

r
= )Cq(k) (,

.
:

)(k

Tq . |j, mi

.|k, qi |j, mi
)(k

Tq |j, mi |j, mi .|k, qi

)(k

: Tq |j, mi :
DTq(k) |j, mi = DTq(k) D D|j, mi
!

 X
)(j
)(k
0
=
DTq D
Dm0 m |j, m i
m0
)(k) (j
Dq0 q Dm0 m Tq(k) |j, m0 i

XX
m0

q0

.|k, qi |j, mi


)(k

Tq

. :
)(k

= hj 0 , m0 |Tq |j, mi m0 = m + q .|j k| j 0 j + k

6 0 :
: ,CG
)(k

Tq |j, mi |j, mi .|k, qi



)(k

Tq CG :
)(k

) :(W igner Eckart Tq .

| jmi " ) j, m ( )
, ( ,:
1
h 0 j 0 ||T(k) || jihkjqm|j 0 m0 i
2j 0 + 1
29

= h 0 j 0 m0 |Tq(k) | jmi

 h 0 j 0 ||T(k) || ji ) T(k 0 , , j 0 , j
,q m .m0

)(k

Tq

CG ) q k .(k
)(k

: , Tq | jmi
.|k, qi |j, mi ,
J2 ,Jz ,CG :2.1
hkjqm|jtot mtot i Tq(k) | jmi

= |jtot mtot i

q,m

) (:
hkjqm|jtot mtot i |jtot mtot i

= Tq(k) | jmi

jtot ,mtot

| h 0 j 0 m0:
hkjqm|jtot mtot i h 0 j 0 m0 |jtot mtot i

)h 0 j 0 m0 |T (k
= q | jmi

jtot ,mtot

|jmi h 0 j 0 m0 |jtot mtot i

jtot = j 0 .mtot = m0 , ) m0 ,
:(~ = 1
h 0 j 0 m0 |J+ J |j 0 m0 i
)j 0 (j 0 + 1) m0 (m0 1
h 0 j 0 m0 |J2 + Jz Jz2 |j 0 m0 i
=
)j 0 (j 0 + 1) m0 (m0 1


0
j (j + 1) + m0 m02 h 0 j 0 m0 |j 0 m0 i
=
)j 0 (j 0 + 1) m0 (m0 1
0 0 0
= h j m |j 0 m0 i

= h 0 , j 0 , m0 1|, j 0 , m0 1i

,h 0 , j 0 , m0 1|, j 0 , m0 1i = h 0 j 0 m0 |j 0 m0 i , ,m0
,.

) ( : V J . ) V(1 )J(1
) (1 V J .2.18:
hj, m|J V|j, mi
hj, m0 |Jq(1) |j, mi
)~2 j(j + 1

30

= hj, m0 |Vq(1) |j, mi

 ::
1
(J+ V + J V+ ) |j, mi
2
= m~hj, m|Vz |j, mi
~p
+
j(j + 1) m(m 1)hj, m 1|V |j, mi
2
~p
+
j(j + 1) m(m + 1)hj, m + 1|V+ |j, mi
2

hj, m|J V|j, mi = hj, m|Jz Vz +

W igner Eckart
hj, m|Vz |j, mi
hj, m 1|V |j, mi
hj, m + 1|V+ |j, mi
) m (j ,hj||V(1) ||ji:
hj, m|J V|j, mi = Cjm hj||V(1) ||ji

)(2.19

Cjm m J V , .Cj
V = J 2.19:
hj, m|J2 |j, mi = Cj hj||J(1) ||ji

)(2.20

W igner Eckart:
hj||V(1) ||ji
hj||J(1) ||ji

)(1

hj, m0 |Vq |j, mi

)(1

hj, m0 |Jq |j, mi

2.19 2.20 :
)(1

hj, m|J V|j, mi

hj, m|J2 |j, mi

hj, m|J V|j, mi

)~2 j(j + 1

hj, m0 |Vq |j, mi

)(1
hj, m0 |Jq |j, mi

)(1

hj, m0 |Jq |j, mi.


: W igner Eckart "
" " ".

, , ,
) .(Lie Groups/Lie Algebras )
(W igner Eckart
Lie Groups, Lie Algebras and Representations .Brian Hall
31

2.7

.1 ,
,'.
.2 " ,
,L21 , L22 , L1z , L2z
.L21 , L22 , L2 , Lz
.3 ) .Clebsch Gordan (CG
, .
.4 .
.
.5 ,
. ,
j .
.
.6 , )
) ( ,
(.
.7 .
.8
) (.
.9 ,
.CG .W igner Eckart

32

3.1

. ,
. ,
. ) (
. )
( .

3.2

,H
:
)(3.1

H|ni = En |ni

, , .

)(3.2

H = H0 + V

H0 ,
H0 .  1 " " V , "" H
"".
H0 ,
|n(0) i

)(0

.En

,H |ni .En
33


n:
|ni = |n(0) i + |n(1) i + 2 |n(2) i + ...

)(3.3

En(0) + En(1) + 2 En(2) + ...

En

3.2 3.1:

 


(H0 + V ) |n(0) i + |n(1) i + ... = En(0) + En(1) + ... |n(0) i + |n(1) i + ...
, k :k
: H0 |n(0) i = En(0) |n(0) i

: H0 |n(1) i + V |n(0) i = En(0) |n(1) i + En(1) |n(0) i

)(3.4
)(3.5

En(2) |n(0) i

)(3.6

En(1) |n(1) i

En(0) |n(2) i

=i

)(1

i + V |n

)(2

: H0 |n
.
.
.

.
.
.

hn(0) |ni = 1 .,
= 0 ) (3.3 ,hn(0) |n(0) i = 1
hn(0) |n(i) i = 0 .i 6= 0
3.4 ) ( .
3.5 | ) hn(0:
hn(0) |En(0) |n(1) i + hn(0) |En(1) |n(0) i
En(0) hn(0) |n(1) i + En(1) hn(0) |n(0) i
)(3.7

hn(0) |V |n(0) i

= hn(0) |H0 |n(1) i + hn(0) |V |n(0) i

= En(0) hn(0) |n(1) i + hn(0) |V |n(0) i
=

) En(1

. ,
,|n(1) i |m(0) i H0 :
X
= |n(1) i
hm(0) |n(1) i |m(0) i
)(3.8
m6=n

m 6= n hn(0) |n(1) i = 0 .
3.5 | )) hm(0 (m 6= n:
hm(0) |H 0 |n(1) i + hm(0) |V |n(0) i = hm(0) |En(0) |n(1) i + hm(0) |En(1) |n(0) i
)(0
Em
hm(0) |n(1) i + hm(0) |V |n(0) i = En(0) hm(0) |n(1) i + En(1) hm(0) |n(0) i


)(0
En(0) Em
hm(0) |n(1) i = hm(0) |V |n(0) i
)(3.9

)(3.10

hm(0) |V |n(0) i
)(0

)(0

En Em

= hm(0) |n(1) i
)(0

6= Em

)(0

,En ,

|n(0) i |m(0) i . ,
.
34

3.2.1

, 3.10 ,3.8 :
|m(0) i

)(3.11

X hm(0) |V |n(0) i
)(0

)(0

En Em

= |n(1) i

m6=n

" 3.6 | ) ,hn(0 :3.11



X hm(0) |V |n(0) i2
)(2
= En
)(3.12
)(0
)(0
En Em
m6=n
, . ,
.
,hn(0) |V |n(0) i hm(0) |V |n(0) i
)(0

)(0

.hm(0) |V |n(0) i  En Em

V .
:3.12
.1 ) ,(n = 0
)(0

) < Em

)(0

E0 ,(m > 0 3.12 .

.
.2 ) V (hm(0) |V |n(0) i
, ) n (
.
.3 "" ) , (
) n ( , .
"" , .
.

3.2.2

)(0

)(0

.3.9 ? ?En = Em
, hm(0) |V |n(0) i = 0 :


)(0
0 = En(0) Em
= hm(0) |n(1) i = hm(0) |V |n(0) i
6 0
)(3.13
, V ) (m 6= n .
, ,V
, . , ,
, .
35

 .
:H0
|0(0) i, |1(0) i, |2(0) i, |3(0) i, |4(0) i, |5(0) i, |6(0) i, ..., |n(0) i, ...
. |2(0) i, |3(0) i, |4(0) i


)(0
)(0
)(0
.E2 = E3 = E4 D = span |2(0) i, |3(0) i, |4(0) i
" " . ,|2(0) i, |3(0) i, |4(0) i
,D
)(0

)(0

)(0

,|2 i, |2 i, |2 i ,D ) ( V
. :
)(0

)(0
)(0
)|0(0) i, |1(0) i, |2(0
i, |6(0) i, ..., |n(0) i, ...
i, |2 i, |2 i, |5

, H0 , ,
?H0 , "" .
. .|2(0) i, |3(0) i, |4(0) i
D ,H0
)(0

)(0

)(0

) |2 i, |2 i, |2 i
.(V
,

)(1

)(1

)(1

,E2 , E3 , E4

3.7 .
? ,

)(0

)(1

6= E4

= E4

)(1
E3

)(0

=6

)(0

= E3

E2 ,

)(1
E2

:
)(1

)(0

)(1

)(0

)(1

)(0

E2 + E2

E2

E3 + E3

E3

E4 + E4

E4

" " . ,
, .
, .
)(0

En k

, " .
n
ok
)(0
. |ni i ,

i=1
n
ok
)(0
)(0
hni |V |nj i , .3.13
i,j=1

. , k .
)(0

)|n(0
i, |n i, ...
|
{z
}
k eigenstates

36

n
ok
)(0
. |ni i

)(1

i=1

En

) (3.7 ,
.
) ( ,
? , ,
.|1(0) i, |2(0) i..., |k (0) i , ) (
)(0

= ... = Ek

)(0

= E2

)(0

)(0

,E1 .E1..k

" 3.5 | ) .hm(0 ,

:
.1 1 m, n k:
)(1

+ hm(0) |En |n(0) i

)(0
hm(0) |En |n(1) i

)(1

= hm(0) |H 0 |n(1) i + hm(0) |V |n(0) i

)(0

)(0

Em hm(0) |n(1) i + hm(0) |V |n(0) i = En hm(0) |n(1) i + En hm(0) |n(0) i



)(1
)(0
)(0
Em En hm(0) |n(1) i + hm(0) |V |n(0) i = En mn
)(0

)(0

)(0

, ,1 m, n k ) Em = En ,(E1..k
:
)(3.14

)hm(0) |V |n(0) i = En(1) mn (1 m, n k

3.6 | ) ,hm(0:
)(3.15

)hm(0) |V |n(1) i = En(1) hm(0) |n(1) i + En(2) mn (1 m, n k

3.15 :
k
X
X
hm(0) |V |i(0) ihi(0) |n(1) i +
hm(0) |V |i(0) ihi(0) |n(1) i
i=1

i>k

hm(0) |V |i(0) ihi(0) |n(1) i

= hm(0) |V |n(1) i

i+

)(1

|n

)(0

ihm

)(0

|V |m

)(0

hm

)(1
Em
hm(0) |n(1) i

i>k

|V |i(0) ihi(0) |n(1) i

)(0

hm

i>k

3.15:
X
=
)hm(0) |V |i(0) ihi(0) |n(1) i (3.16

)(1
En(1) Em
hm(0) |n(1) i + En(2) mn

i>k

.2 ) m > k n( :
)(3.17

)(m > k

hm(0) |V |n(0) i
)(0

)(0

En Em

37

= hm(0) |n(1) i

 3.17 hm(0) |n(1) i ,m > k

3.16:
)(3.18

|V |i(0) ihi(0) |V |n(0) i

)(0

X hm

)(0

)(0

Em Ei

)(1
En(1) Em
= hm(0) |n(1) i + En(2) mn

i>k

, 3.17 hm(0) |n(1) i .m > k ,3.8

hm(0) |n(1) i .1 m, n k .3.18
:m 6= n
)(1 m, n k

)(0

|V |n

)(0

ihi

)(0
Ei

)(0

|V |i

)(0

X hm

)(0
Em

)(1
Em i>k

)(1
En

= hm(0) |n(1) i

m = n :


X hn(0) |V |i(0) i2
)(2
= En
)(0
)(0
i>k En Ei
V ,D .
. , ) D ,(D1
:
.1
. ,3.18
)(1

= Em

)(1

En .m 6= n

, , .D1
.2 V1 ,D1 V1 .
.
V1 .V
, .
, . ,
.

3.2.3

" " Z .
:
Ze2
p2

2me
r

)(3.19

= H0

:
2

Z
n

1
En(0) = me c2
2

38

3.2.3.1

":
q
p2
p4
2
2
(pc) + (me c2 ) me c2

2me
8m3e c2

p4
8m3e c2

H0 .3.19 .:
D 4 E
p

 2
8m3e c2
p
1
D 2 E

p
2me 2me c2
2me

:
1
hEk i = hEp i
2
:
= hEtot i

)En(0

= hEk i + hEp i
= hEk i
:

2
1
2me c2

)En(0

8m3e c2

(Z)2
0.53 104 Z 2
.Z

39

) (p2

p2
2me

 :
= hn(0) |V |n(0) i
p4
= hn(0) | 3 2 |n(0) i
8me c
p4
= hnlm| 3 2 |nlmi
8me c

2
Ze2
1
|hnlm
H
+
|nlmi
=
0
2me c2
r
1
2Ze2
Z 2 e4
=
hnlm|H02 +
H0 + 2 |nlmi
2
2me c
r
r


2
1
1
1
)(0
)(0
2
2 4
=
E
|nlmi
+
2E
Ze
|hnlm
|nlmi
+
Z
e
|hnlm
n
n
2me c2
r
r2


1
(Z)4
1
3
=

1
2
3
2me c
n
4n
l+ 2

)En(1

.l , , l ,
, l . , m
.

3.2.3.2

E = , ""
)) B = 1c (v E ( . ,
e~g
S
. = 2m :
ec

e~g
)S (v E
2me c2
e~g
))S (p (r
2m2e c2
e~g
)1 d(r
)S (p r
2
2
2me c
r dr
e~g
)1 d(r
SL
2m2e c2
r dr

=
=
=

, " .T homas:
)(3.20

e~g
)1 d(r
SL
4m2e c2
r dr
A(r)SL

B =

) (S ) .(L
, ) J2 ,Jz ,L2 ,S2 .(J L + S
) |n, j, mj , l, si
40

 ( . :
hn, j, mj , l, s|A(r)SL|n, j, mj , l, si


1
hn, j, mj , l, s|A(r) J2 L2 S2 |n, j, mj , l, si
2
Z
1
2
[j(j + 1) l(l + 1) s(s + 1)] r2 Rnl
(r)A(r)dr
2

)(3.21

1
2

1
2

)En(1

=
=

l + ) l 21 ,(2.2 :

= ,s j
(


Z
l
j = l + 21
1
2 2


=
r Rnl (r)A(r)dr
2
l 1
j = l 12

)En(1

, j .
" " .F ine Structure ,
mj .
,j > 0 .l 6= 0 ,
,3.20 ) A(r 1 ,3.21:
(


l
j = l + 12
g
1
2
4


= me c (Z) 3

)(3.22
4
)n l(l + 1)(2l + 1
l 1
j = l 21

)En(1

.l = 0 , l = 0 3.22
1
2

,j = l + l l , .l = 0

, . l = 0
.Darwin
) (
.(Z)4

3.3

H0""
. .
.
:
)(3.23

h|H|i
h|i

= ]E[

)
(.
1 A(r) > 0

41

 : ] E[ .H
] E[ .

. .
: ] E[ .
:
0

]) E[(x
]) E[(x ) + (x x)] E[(x
lim
0
)(x

, ) (x0 x
, E .
E:


d
= hE[], f i
] E[ + f
d
=0
.f
, ] E[ ,
:
0

]) E[(x
=0
)(x
) ( . .
" ,
, .
: 3.23:
E[]h|i = h|H|i
,:
) (E[]) h|i + E[] (h|i) = (h|H|i
, (E[]) = 0 H ) (H = 0
:
E[] (h|i + h|i) = h|H|i + h|H|i
:
)(3.24

h|H E[]|i + h|H E[]|i = 0

, ,i :
)(3.25

hi|H E[]|i + h|H E[]|ii = 0

42

 i 3.25 3.24 :
H|i E[]|i = 0
, H ].E[

: 0 H ] E0 = E[0 . E[] E0 ,
. = 0
: 3.23:
h|H E0 |i
h|i

)(3.26

= E[] E0

:H
X
= |i
hn |i |n i
n

3.26:
X h|H E0 |n i hn |i
h|i
n
X
h|n i hn |i
=
) (En E0
h|i
n
=

E[] E0

||hn |i
0
h|i

) (En E0

,En = E0 . = 0

,
) " "( . ,
) , , ,'( . ,
) = (a, b, c, ... a, b, c, ...
] E[.

3.3.1

+ V

p2
2m

= ,H:
|x| < a

|x| > a

43

(
= V

2 2

~
,( 8a
) 2 m

. ,
.|x| a
, :
|x| a

a 2 x2

|x| > a

(
= )(x

:
Ra

d2


a2 x2 dx
a2 x2 dx
2
= ]E[
Ra
2
(a2 x2 ) dx
a
   2 2
10
~
=

2
8a2 m
a

10
2

1.0132

~2
2m

:
|x| a

a x

|x| > a

(
= )(x

:


~2
4ma2



)( + 1)(2 + 1
)(2 1


= ]E[

. = 1+2 6 1.72 :
 !  2 2
~
5+2 6

= ]E[
2
8a2 m
0.3% !

3.4

.1
) ( .
.2 ,
.
.3 ,
. .
.

44

 .4
.
.5 .
.

45

4.1

" , " .
,
. " ".

4.2

: H . T H H
,:
)(4.1

T 1 HT = H

" H "T " H ."T

: T ,H .[T, H] = 0
: 4.1 T :
HT = T H

46

4.2.1

: H H .E , T
H .E
: :
)T (H

)T (E

)H(T

)= E(T


: H E ,
.T
: H:
H = E
:
)H(T ) = E(T
,E :
}T span {
:
T =
.

: Tinv .
2

) .Tinv (r) = (r) (Tinv ) = I , I ( .

Tinv 1 .1 , ,
.
: .
: .E E ,
) Tinv Tinv
( . Tinv = .Tinv = (r) = (r) ,
) .(r) = (r , .
47


.
: L2 , Lz
) " "( . ,
,l .
: L .Tinv
= r

Tinv rTinv

= p

Tinv pTinv

= Tinv (r p) Tinv
)(r p

Tinv LTinv

= L
= Tinv

) ,(Tinv .(Tinv ) = I,
2

l, m L , Lz ,
. .m :
)Tinv Yl,m1 () = tl,m1 Yl,m1 (
:
)T L Y (
p inv l,m
)l(l + 1) m(m 1
)L Tinv Yl,m (
= p
)l(l + 1) m(m 1
)L tl,m Yl,m (
= p
)l(l + 1) m(m 1
)= tl,m Yl,m1 (

)Tinv Yl,m1 (

:
tl,m1 = tl,m


Yl,m ,(1)l Yl,m l,
.
48

4.2.2

: T ,H T . T
, .
: .[T, H] = 0 :
i
T
h[T, H]i + h
i
~
t
0+0
0

d
= hT i
dt
=
=

hT i .


4.3

Bloch

).Ta (r) = (r + a
: a:
i

Ta = e ~ ap

)(4.2

: " Ta = e ~ ap :


i
i
1 i
= )e ~ ap (r
)1 + a p + ( a p)2 + ... (r
~
~ 2


1 2
=
)1 + a + a 2 + ... (r
2
1
= (r) + (r) a + 2 (r) a2 + ...
2
)= (r + a
i

, e ~ ap .a

, p "" , L
"" )' 2.6.1" .(20
[p, Ta ] = 0 : .
,p .eikr:
)= eik(r+a
= eika eikr
49

Ta eikr

 eikr Ta .eika
, ei(k+Q)r Q a = 2n
.ei(k+Q)a = eika
.Ta
) :(Bloch ) u(r ,a )eikr u(r
) " " " "( Ta .eika
:
)eik(r+a) u(r + a


)eika eikr u(r



= )Ta eikr u(r
=


.
, .
) Ta a ( . ,
.
) ,
( .
, . ,
, ?
.

4.4

Tij
i .j ,
" . , :
p2 2
e2
p1 2
+
+
2me
2me
| |r1 r2

=H

pi ) ,(i = 1, 2 ri .
1 2 . ,
.
: H , Tij
i .j , .
50

 : .Tij
2

) (Tij ) = I , I , ( , Tij 1
.1 ,:
Tij =
:
Tij =
.

, ,
.
.
" ) ,(,
" )
( . "
. , , ) (
) ( .Tij
,
. )
(.

4.4.1

P auli

, .
" .

,{|ni}n=0 .{|mi}m=0
.

{|ni|mi}n,m=0 .{|n, mi}n,m=0

n 6= m |n, mi
. ? ,
, |n, mi ) |m, ni
.(En + Em

)(4.3

1
) (|n, mi + |m, ni
2
51

 ,
)(4.4

1
) (|n, mi |m, ni
2

)
(.
|m, ni |n, mi .
1 ,m 2 .n ,
1 ,n 2 .m
, .
. , ,
. 4.3 4.4 :
1
]) [n (1)m (2) n (2)m (1
2
n m
. , ) 2 (1 " 1 ,"2
" 2 " ."1
: N , } {1 , 2 , ..., N N .

.
, ,
1
]) [1 (1)2 (2)3 (3) 1 (2)2 (1)3 (3
2
1 ,2 ) (
1 3 2 .3 ,
)[1 (1)2 (2)3 (3) 1 (2)2 (1)3 (3
)(4.5

1
6

)+1 (3)2 (1)3 (2) 1 (1)2 (3)3 (2

])+1 (2)2 (3)3 (1) 1 (3)2 (2)3 (1

. ,
. ,
:
: V ,n) Altk (V k
.V:
!n
!)k!(n k

!
=

= ) dim Altk (V

52

 } V = span {1 , 2 , ..., N .k = n

, .
: N } {1, 2, ..., N
) .(1, 2, ..., N
N .SN ! .|SN | = N
: .N ,i < j )) ((i), (j ""
) (i) < (j "" ).(i) > (j
: .N s .
(1)s ).sign(
,
2

)(1

)(2

)(3

) 1 1 ,(2
.1
)( N
N :
)(4.6

1
= a
)) sign() 1 ((1)) 2 ((2)) N ((N
N ! SN
X

)) 1 ((1 1 ) ,(1
, ) ! N(.
4.5 , 3! = 6.
a
, a .
4.6 ,
4.6

 ) 1 (N

 ) 2 (N

.

.

.

 ) N (N

)1 (2

)2 (2

..

.
.
.

)N (2


) 1 (1


)1  2 (1
 = a
.
.
 !N
.

) (1
N

.Slater
, 4.6
,E1 + ... + En a ,
.
53

 ) (:
.1 .
.2 .
:
.1 , .i = j
. a = 0
.
.2 ,
p .q
. 1 .
:
, .
, .
,
, .
.
, , :
N1 !N2 ! NN ! X

)) 1 ((1)) 2 ((2)) N ((N

!N
SN

= s

P
Ni ) i .( Ni = N
i .s

4.5

.1 ,
.
.2 , , .
.3 , .
.4 .
.5 .
.
54

 .6 "
.Slater
.7 P auli ,
.

55

5.1

)
Z ( .
.
p1 r1 ) ,(1
p2 .r2 , :
)(5.1

5.1.1

p2 2
Ze2
Ze2
e2
p1 2
+

+
2m
2m
| |r1
| |r2
| |r1 r2

=H

, .
, . ,
.
)
(:
)n1 l1 m1 (1)n2 l2 m2 (2
L2 ) Lz ( ,
, :
)n1 lm (1)n2 lm (2
1 .
56

 :
1
])a = [n1 lm (1)n2 lm (2) n1 lm (2)n2 lm (1
2
: " / "
" /".
: .l n 1
: a " . a
) n1 = 1 .(n2 = 1
: "" ,1Ry = 13.6eV ,
. n1 = 1 = ) n2
( . ) :(Z = 2
Z2
Z2

n21
n22
4
=
1
= 4Ry
=

= En1 =1,n2

n1 = 2 .n2 = 2 ) , :(Z = 2
Z2
Z2

n21
n22
4 4

4 4
2Ry

En1 =2,n2 =2

=
=

. , !
, ,
, .

. ,
.
S2 Sz , )
(t ) .(s
: )
( , ,
,.
57

 :
1
])s = [n1 lm (1)n2 lm (2) + n1 lm (2)n2 lm (1
2
)
(:
a t

)(5.2

) (:
s s

)(5.3

s ) (
) , , (.
5.2 orthohelium 5.3 .parahelium
, ,n = 1
)
:(n1 , l1 , m1 = n2 , l2 , m2 = 1, 0, 0
)(5.4

= 100 (1)100 (2) s

groundstate

n = 1 ,li = mi = 0
? :
1
)s = (| i | i
2
, ,
) ( , .
:
Z2
Z2
2
2
n1
n2
4 4

1 1
8Ry

108.8eV

En1 =1,n2 =1

,78.975eV
.
, ,
n1 = 1 ) n2 = 2 (
l = 0 .l = 1:
)(5.5

1
[100 (1)200 (2) 100 (2)200 (1)] t
2
58


)(5.6

1
[100 (1)21m (2) 100 (2)21m (1)] t
2

:
Z2
Z2

n21
n22
4 4

1 4
5Ry

68eV

En1 =1,n2 =2

,
, )
) ( .(S
5.5 ,5.4 5.6 S2 ,Lz ,L2
.Sz ,
H . , 5.55.6
) (:

 )100 (1) (1) 100 (2) (2

 )2lm (1) (1) 2lm (2) (2







 1

2


)1  100 (1) (1) 100 (2) (2

)2  2lm (1) (1) 2lm (2) (2

.S 2 5.5 ,5.4 ,5.6

, .S 2

5.1.2

e2
| |r1 r2

, .

5.1.2.1

,
.
) , ,1

59

 , (:
e2
|groundstate i
| hgroundstate
| |r1 r2
Z
1
e2

]) [100 (r1 )100 (r2 ) + 100 (r2 )100 (r1

| |r1 r2
2
3
3
[100 (r1 )100 (r2 ) + 100 (r2 )100 (r1 )] d r1 d r2
e2
2
|100 (r2 )| d3 r1 d3 r2
| |r1 r2

...
Z

|) |100 (r1

)(1

E0

=
=

. Gasiorowicz
) 18" 297 ( , :
5
)(1
E0 = Ry = 34eV
2
108.8 + 34 = 74.8eV
.78.975eV
, .
," ,
, .
.
) ,l l = 0 :(l = 1
)(5.7

1
[100 (1)2lm (2) 100 (2)2lm (1)] t
2

)(5.8

1
[100 (1)2lm (2) + 100 (2)2lm (1)] s
2

, . , , ,

e2
| |r1 r2

. | |r1 r2
.D , Lz L2
.
,
) ,5.7
:(5.8
Z
1
e2
2
|) |100 (r1 )nlm (r2 ) 100 (r2 )nlm (r1
d3 r1 d3 r2
= )En(1
2
| |r1 r2
Z
e2
2
2
=
|) |100 (r1 )| |nlm (r2
d3 r1 d3 r2
| |r1 r2
Z
e2

100
(r1 )nlm
) (r2 )100 (r2 )nlm (r1
d3 r1 d3 r2
| |r1 r2
Jnl Knl
60

:
e2
d3 r1 d3 r2
| |r1 r2

|) |100 (r1 )| |nlm (r2

= Jnl

Direct Integral
e2
d3 r 1 d3 r 2
| |r1 r2

100
(r1 )nlm
) (r2 )100 (r2 )nlm (r1

Z
= Knl

Exchange Integral "/ " . J K

,m .
2

.hl1 , l2 , l, m 1| |r1er2 | |l1 , l2 , l, m 1i = hl1 , l2 , l, m| |r1er2 | |l1 , l2 , l, mi :

: :L
2

hl1 , l2 , l, m|L |r1er2 | L |l1 , l2 , l, mi

)l(l + 1) m(m 1

e2
|hl1 , l2 , l, m 1
= |l1 , l2 , l, m 1i
| |r1 r2

hl1 , l2 , l, m| |r1er2 | L L |l1 , l2 , l, mi

)l(l + 1) m(m 1


2
hl1 , l2 , l, m| |r1er2 | L2 Lz L2z |l1 , l2 , l, mi
l(l + 1) m m2
e2
|hl1 , l2 , l, m
|l1 , l2 , l, mi
| |r1 r2

=
=
=


) , (
.

5.1.2.2

.
. , ,Z = 2
Z ] .E[ :
s
s
3
3
Zef f
Zef f
Zef
Zef
f a
f a
r1
r2
0
0
= ) (Zef f
e

3
3
a0
a0
3
Zef f
Zef
f a
) (r1 +r2
0
e
a30

61

 a0 .Bohr ]) E[(Zef f 5.1:

d
]) E[(Zef f
dZef f

d
= h(Zef f )|H|(Zef f )i
dZef f
.
.
.

5
16
1.6875

= Z

Zef f

:
2
2
Zef
Zef
f
f

n21
n22

En1 =1,n2 =1

2
2Zef
f

= 77.5eV
.78.975eV
?Zef f = 1.6875
. , 1.6875e
2e ) (e .

. ) 50( '
.
" ) W EIZAC .(5.1

5.2

, :
 X
X  pi 2
Ze2
e2
=H

+
)(5.9
2m
| |ri
| |ri rj
i
i<j

. ,
.
, . ,
?
:
) (1, 2, ...N ) = 1 (1)2 (2) N (N
62

 :5.1 ,W EIZAC .

:
) i (i) = i (ri )i (msi
? ,
, ] E[ .
. ] E[.
" ."Hartree

. ,
. , .
, " ."Hartree F ock
.

63

5.2.1

5.2.1.1

'

) f (r Rn .R f k
.gk (r) = 0 :
)k gk (r

(r, ) f (r) +

k " '" . :
r f (r) = 0

)(1

gk (r) = 0

)(2

:
0

:
)k r gk (r

r f (r) =

r = 0

gk = 0

= 0

f , .
] E[ f
".

5.2.1.2

] E[ .
" ] E[ ," ) ) = F (1 , 2 , ..., N
.(
: ] E[i i .i = 1, ..., N
j:
]) E[i (x0 ) + ij (x0 x)] E[i (x0
]) E[i (x0
lim
0
)j (x

, . ) (x0 x
, E .
E:


d
= hE[i ], f i
] E[i + f
d
=0
64

 .f
,
. .

5.2.2

Hartree

, :
) (1, 2, ...N ) = 1 (1)2 (2) N (N
:
) i (i) = i (ri )i (msi
] E[ :
Z
2
|i (ri )| d3 ri = 1
 2
2





i ( 1 ) + i (+ 1 ) = 1



2
 2
, ] E[ ) 5.9
:(
= h|H|i
!
2 2
2
XZ
~

Ze
=
i (r)

i (r)d3 r
2m
r
i
XZ
e2
+
) i (r1 )j (r2
j (r2 )i (r1 )d3 r1 d3 r2
|r

r
|
1
2
i<j

]E[

,i ' .i
:
)(5.10

#
2 3
|i (ri )| d ri 1
=0

"

Z
i

E[]

) '(.
,
. , )
( Gasiorowicz ) 19" 309 ( .
5.10 :Hartree
#

)(5.11

"

Ze2
~2

)+ Vi (r) i (r) = i i (r
2m
r
65

:
2

e
2
|j (r0 )| d3 r0
| |r r0

XZ

= )Vi (r

j6=i

, ,
.
) i (r ,
) Vi (r ,i ) Vi (r )...i (r
" , ) i (r
, ) Vi (r 5.11 ) i (r.
) Vi (r ,' ' ,
.
, .
, i ,
. , i
, ,? ,
i 5.11 ,
) Vi .(i
Hartree F ock .

5.2.3

Hartree F ock


 ) 1 (N

 ) 2 (N

.
..

.
.

.

 ) (N
N

,:

) 1 (1) 1 (2


)1  2 (1) 2 (2
 = ) (1, 2, ..., N
.
.
.
.
 !N
.
.

) (1) (2
N

, :
) i (i) = i (ri )i (msi
:
= h|H|i
!
2
XZ
Ze2
~2

i (r)d3 r
=
i (r)
2m
r
i
XZ
e2
2
2
+
|i (r1 )| |j (r2 )| d3 r1 d3 r2
|r

r
|
1
2
i<j
XZ
e2

msi msj i (r1 )i (r2 )j (r2 )j (r1 )d3 r1 d3 r2

|r

r
|
1
2
i<j
66

]E[

l
8

k
7

i
6

h
5

f
3

g
4

p
1

d
2

s
0

x
l

:5.1 l .
Stupid P hysicists , .

5.11 :
i
)+ Vi (r) i (r

Ze2
r

~2m

XR
2
e
0
3 0

j (r0 ) |rr
)= i i (r
0 | i (r )j (r)ms ms d r
i
j
j

:
e2
2
|j (r0 )| d3 r0
| |r r0

XZ

= )Vi (r

i
N

) {i }i=1 (.

5.3

5.3.1

" ,n ,l m
. .
: .n
: n .l
nxe x ) l (5.1
e .
"".
: l ,n .m
, ,
.
) 2(2l + 1 , " 2n2
, .
: ,Hartree F ock
, .
67

 .
: i ,Hartree F ock
, L2 ,Lz
.Ylm

"
. .

) (nxe .
. , ,
.

5.3.2

L . , S ,
J . , S ,LJ
.
, :
)(5.12

LJ

2S+1

L " , " ,5.1

. 5.12 Spectral T erm "
".
, M ,0 ,0
.
.
, .

5.3.2.1

.2p2,
n1 = n2 = 2 .l1 = l2 = 1
?
L = l1 + l2 ) L = 0, 1, 2 ,(2.2
.L = S, P, D , , s1 = s2 = 21
.S = 0, 1 L S
68

 . , ,l
.
, ) ,S = 1(
, , ) ,S = 0(
. , L .
: ,l1 = l2 l
. |l, m = li , ) l m(
. |l, m = li , ) l m(
.
: |l, li L .|l, l 1i
L = L1 + L2 ) (Tij |l, l 1i
.|l, li L l
.

l = l1 + l2 ,
l = l1 + l2 1 , )
(... .l = l1 l2 = 0
, l = l1 + l2
|l1 , m1 = l1 i ,|l2 , m2 = l2 i l1 = l2
|l, m = li = |l1 , l2 , m1 = l1 , m2 = l2 i
.
L = D , L = P
L = S . :
SJ ,1 PJ ,0 DJ

J ,2.2 :
S0 ,3 P0 ,3 P1 ,3 P2 , 1 D2

, ,
l . .
: 2p 2(2l +1) = 23 = 6 ) 2
.(m 2 ,

69

 2 6
:
!

= 15

.
: , l1 = l2 = 1 = L
) 0, 1, 2 ,(2.2 .L = S, P, D ,
1
2

= s1 = s2

.S = 0, 1 , ) ,(ml , ms :
) (c) = (1, 12

) (b) = (0, 12

) (a) = (1, 21

) (c0 ) = (1, 21

) (b0 ) = (0, 12

) (a0 ) = (1, 12

: , )
( ,
Ml Ms:
State

) (Ml , Ms
)(1, 0

)(2, 0

)(1, 1

) (Ml , Ms

) (c) + (b
) (c) + (c
) (a ) + (b

State
0

) (b) + (a

)(1, 0

) (b) + (b

)(0, 0

) (Ml , Ms
)(2, 0
)(1, 0

)(1, 0

)(0, 0

) (b) + (c

State
0

) (a) + (a
0

) (a) + (b
0

) (a) + (c

)(0, 1

) (a ) + (c

)(1, 1

)(b) + (c

)(1, 1

)(a) + (b

)(1, 1

) (b0 ) + (c0

)(0, 0

) (c) + (a0

)(0, 1

)(a) + (c

: :
Ml = +2
1

Ml = +1

Ml = 0

Ml = 1

Ml = 2
Ms = 1
1

Ms = 0
Ms = +1

: 1:
Ml = +2

Ml = +1

Ml = 0

Ml = 1

Ml = 2

Ml = +1

Ml = 0

Ml = 1

Ms = 1

Ms = 0

Ms = +1

70

Ms = 0

Ml = 0
Ms = 0

: :
.1 .S = 0, L = 2 J
,2 .1 D2
.2 .S = 1, L = 1 J
,0, 1, 2 .3 P0 ,3 P1 ,3 P2
.3 .S = 0, L = 0 J
,0 .1 S0
J , , .2.2"
:
D2 ,3 P0 ,3 P1 ,3 P2 ,1 S0

" "
M , .2J + 1 :
1 + 5 + 1 + 3 + 5 = 15
.
) (.
, .Hund

5.4

Hund

Hund .
:
: S , L .
: S .
: S , L .
: , J
. ,
J .
) , ,
, (:
71

 : S
) ( .
, , .
: L .
.
.
, .
, ,
.
: nle . ) ,D = e (2l + 1
,2S+1 LJ ,:
1
)|(e D |D
2
L = |D| S
(


1
= (D
)6 0
L 1+ D
= J
S
)(D = 0
S

: :
:D < 0 .1
) ,2(2l + 1
.2l + 1 , ,D < 0
. , +1/2
) ( . :
1
e
2
1
)(e D + D
2
1
])[e D (D
2
1
)|(e D |D
2

=
=
=

L ml ,
ml ) (:
ml

= L

occupied states

)(l n

e1
X
n=0

72

 :
e
2

])[l + l (e 1

= L

1
(2l + 1 e) e
2
DS

|D| S

, J ,J = L S:

LS
L
L+
D


1
L 1+
D

=
=
=

:D > 0 .2
D ,

.
,1/2 :
1
eD
2
1
)(e 2D
2
1
)(e D D
2
1
)|(e D |D
2

=
=
=

n = 0
:
)(l n

D1
X

= L

n=0

D
2

])[l + l (D 1
D
2

)(2l + 1 D

D
)(e 2D

2
1
=
eD D
2
= DS

|D| S
73

Pl

 , , J ,J = L + S
:

L+S
L
L+
D


1
L 1+
D

=
=
=

:D = 0 .3
,:
1
e
2
1
)|(e D |D
2

:
0
|D| S

= L
=

:
SLJ S+L
L = 0:
J =S

5.5

) 3.2.3.2" ,(40
. N
, ,Mi ,Bi
:
)(5.13

N
e~g X
) Si (vi Ei
4me c2 i=1

Mi Bi =

74

N
X
i=1

 Ei .i ,
, .
.
, ,
L) S (.
.W igner Eckart
W igner Eckart q
) ,T(k:
h0 , J 0 , M 0 |Tq(k) |, J, M i hk, q, J, M |J 0 , M 0 i
q M .M 0
(k = 1) 1:
h0 , J 0 , M 0 |Tq(1) |, J, M i h1, q, J, M |J 0 , M 0 i

J:
q |, J, M i h1, q, J, M |J 0 , M 0 i
h0 , J 0 , M 0 |J
, J ,0 , J 0 , ,M ,q M 0
1 )
J ,0 , ,(J 0:

T(1) J

)(5.14

) 2.18" (28 1
. 5.14 :

VJ

)(5.15

? , Si 5.13

,S ) (vi Ei

.B , 5.15:
tot
S

L
tot
B
, L .S
:


tot S
tot
I = ALS L

, :
)Isingleelectron = A(r) (L S
75

 I :


tot S
tot
ALS L


1
2 L
2 S
2
ALS J
tot
tot
tot
2

L 2
2 ,J
2
,S
tot
tot
tot
:
)(5.16

1
])ALS [J(J + 1) L(L + 1) S(S + 1
2

, L ,S J
) ( . " "
.
?ALS ,
) (Asingleelectron .
: N .
.ALS > 0 .ALs < 0
: ,
) N .(Si
, Hund ,
.:
tot = N Si
S
, , :
)(5.17

Isingleelectron

N
X

i=1

)(5.18

) (Li Si

N
X

= Asingleelectron

i=1
N

 Asingleelectron X
tot
Li S
N
i=1

 Asingleelectron
tot
Ltot S
N

=
=

:
Asingleelectron
>0
N

= ALS

, 5.18
"" :
X
X
= ) (Li Si
(Li Si )
) (Li Si
i=empty states

i=all states

76

X
i=electrons

 .S = L = J = 0 ,
, " .
:
) tot = N (Si
S
. , :
ALS < 0


.
ALS > 0 , ,3.21 S L ,
J . ,ALS < 0 ,
J.
:
. , ,nd8
) nd2 nd8
nd (.
, , J ,
Jz .J
, ," .
.Zeeman

5.6

Zeeman

.B = B
z
, :
e
)(r v
2c
e

)(r p
2me c
e

L
2me c

77

=
=

Morbital


B

ge e
e
Li +
Si
2me c
2me c

 N
X

= Miorbital + Mispin B

i=1

i=1

e
(L + ge S) B
2me c
e
(Lz + ge Sz ) B
2me c

N
X

=
=

S ,L J , ) MJ
(M . ,
:
hLSJM |Lz + ge Sz |LSJM 0 i
,W igner Eckart
L + ge S J
, S ,L .J
."Land , :
,gLSJ " e
hLSJM |Lz + ge Sz |LSJM 0 i = gLSJ hLSJM |Jz |LSJM 0 i
= gLSJ ~M M M 0
,M .

5.6.1

Land
e

) J (L + ge S :
.1 :
)(L + S) (L + ge S

)J (L + ge S

= L2 + ge S2 + (ge + 1)L S


1
= L2 + ge S2 + (ge + 1) J2 S2 L2
2
ge + 1 2 ge 1 2 ge 1 2
=
J +
S
L
2
2
2
:
ge 1
])[J(J + 1) + S(S + 1) L(L + 1
2

hLSJM |J(L + ge S) |LSJM i = J(J+1)+

78

 .2 :W igner Eckart
X X
hLSJM |Ji |LSJM 0 i hLSJM 0 |Li + ge Si |LSJM i

= hLSJM |J (L + ge S) |LSJM i

i=x,y,z M 0

hLSJM |Ji |LSJM 0 i hLSJM 0 |Ji |LSJM i

X X

= gLSJ

i=x,y,z M 0

= gLSJ hLSJM |J2 |LSJM i

)= gLSJ J(J + 1

:
)J(J + 1) + S(S + 1) L(L + 1
)(ge 1
)2J(J + 1

)(5.19

gLSJ = 1 +

Zeeman
.ge
, S = 0 ,J = L .gLSJ = 1
. Zeeman
,gLSJ > 1 Zeeman ) ,
(.

5.7

.1 .
)( .
.2 )(
.
.3 Hartree
) Hartee F ock (.
.4 .
.5 ),
(
.6 Hund .
.7
,J Hund.
.8 Zeeman ,MJ
g
.
79

6.1

. , .
. , .
, .

.
, ,:
1

1
2
2 Mp v p
1
2
2 me ve

Mp
104
me
:
1
vp

ve
100
, 100 . ,
.
,m p
,r ,M P .R
.

80

6.2

Born Oppenheimer

,Te ,TN
,Vee ,VN N .VeN" :
)(6.1

H = Te + TN + Vee + VeN + VN N

, ,
.R )) (r|R ,
r .(R :
)(6.2

)(Te + Vee + VeN ) (r|R) = E el (R)(r|R

R .
:
)(6.3

)(R) VN N (R) + E el (R

) ( :
)(6.4

)(r, R) = (r|R)(R

:
)(6.5

)H(r, R) = E(r, R

6.3 ,6.2 ,6.1 6.4 6.5:

)(r|R) [TN + (R)] (R) = (r|R)E(R


)(R)2R (r|R) + 2R (R)R (r|R

~2
2MN

R
. ) (r|R : d3 r
)[TN + (R)] (R) = E(R

)(6.6



R
(R) (r|R)2R (r|R)d3 r

~2
2MN



R
2R (R) (r|R)R (r|R)d3 r

~2
2MN

X
N

81

 ).(R
, :
Z
=
(r|R)R (r|R)d3 r
Z
1
=
R 2 (r|R)d3 r
2
1
R 1
=
2
= 0

(r|R)R (r|R)d3 r

, ) .(r|R) = (r R :
Z
Z
~2
~2
= (R) (r|R)2R (r|R)d3 r
(R) (r|R)2r (r|R)d3 r
2M
2M
m el
=
)hE i(R
M kin
el
 hEkin
)i(R
)E el (R)(R

,6.6 :

)TN + V (R) + E el (R) (R) = E(R

, ) E el (R
. .Born Oppenheimer

6.3

H2+

) ( .
) A (B , ,
RA ,RB :
e2
e2
e2
~2 2

+
2m
| |r RA | |r RB
R

=H

| R |RA RB .
) .(6.1
) ,(6.1
.r ,
.RA = RB
, ?
?
, ,r
.
82

 :6.1 H2+

,
. .
:
s
| 1 |rRa A,B
0
= )A,B (r
e
a30
,r
:
]) (r) = C [A (r) B (r
C :
Z

| (r)| d3 r

])|C | [2 2S(R

1
)2 2S(R

| |C

:
A (r)B (r)d3 r

Z
= )S(R

. )
(:
R

e a0

R
R2
+ 2
a0
3a0


1+

= )S(R

A = |Ai B = |Bi :
1
][hA|H|Ai + hA|H|Ai 2hA|H|Bi
)2 2S(R
83

= h |H| i

:6.2 .

,hA|H|Ai = hB|H|Bi:
)(6.7

1
][hA|H|Ai hA|H|Bi
)1 S(R

:
Z
e2
) A (r
A (r)d3 r
| |r RB


R
R
1+
e2 a0
a0

=  (R) h |H| i

e2
R
e2
E1 +
R
Z
A (r)HB (r)d3 r




R
e2
e2
R
S(R)
1+
e a0
E1 +
R
a0
a0

E1 +

= hA|H|Ai
=
= hA|H|Bi
=

E1 ) .(13.6eV
,6.7 :



R
e2
R
1
E1 +
1+
e2 a0
)1 S(R
R
a0





e2
e2
R
aR
0
E1 +
S(R)
1+
e
R
a0
a0

) (R

) .(6.2 ) (+
) ( .bonding orbital ,
) ( ) (R
.anti bonding orbital
84

 ,R = 1.32
.R = 1.06 :
s
| A,B
Zef f Zef f |rR
a0
= )A,B (r
e
a30
.Zef f

6.4

H2

,
. .

6.4.1

:
1
[+ (r1 )+ (r2 )] s
)2 + 2S(R
1
[+ (r1 ) (r2 ) + (r2 ) (r1 )] t
2

)s (1, 2

)t (1, 2

s )
( , t )
(.
, .

6.4.2

Heitler London

:
1
p
[A (r1 )B (r2 ) + B (r1 )A (r2 )] s
) 2(1 + S 2
1
p
[A (r1 )B (r2 ) B (r1 )A (r2 )] t
) 2(1 + S 2

)s (1, 2

)t (1, 2

:
1
)(hAB|H|ABi hAB|H|BAi
1 S2

= s,t hHis,t

,
,

85

 .":
~2 2
~2 2
e2
e2
1
2

2m
2m
| |r1 RA | |r1 RB
2
2
e
e
e2
e2

+
+
| |r2 RA | |r2 RB | |r1 r2 | |RA RB

s,t
Z

A (r1 )B (r2 )HA (r1 )B (r2 )d3 r1 d3 r2

= hAB|H|ABi

2E1 + Q
:
e2
e2
e2
e2

d3 r1 d3 r2 +
| |r1 r2 | |r1 RB | |r2 RA
R
Z
Z
2
2
2
e
e
e2
2
2
2
= 2 A
) (r1
d3 r1 + A
) (r1
B
(r2 )d3 r1 d3 r2 +
| |r1 RB
| |r1 r2
R


2
2
A
(r1 )B
) (r2

= Q

B A
A .B .
.
s,t
Z

A (r1 )B (r2 )HB (r1 )A (r2 )d3 r1 d3 r2

= hAB|H|BAi

2E1 S 2 + A
:


e2
e2
e2

| |r1 r2 | |r1 RB | |r2 RA

Z
=

) A (r1 )B (r2

e2
r1 d3 r2 + S 2
R
Z
e2
) = 2S A (r1
B (r1 )d3 r1
| |r1 RA
Z
2
e2
e2
) + A (r1 )B (r2
B (r1 )A (r2 )d3 r1 d3 r2 + S 2
| |r1 r2
R
3

, ,
.
" :
QA
1 S2

s,t = 2E1 +
86

 .
,R Q , A
.Q ,s < 2E1
) s 2E1 .(R ,s > 2E1
. , Q ,Schwabl
) R Schwabl ,
Q , Q ( . ,
.
R
,R = 0.87 .R = 0.74 Gasiorowicz
50 . .

6.5

. , .
! ,

.
:
"" .
) (methane
) .(CH4 :
1s2 2s2 2p2
, :

1s 2s 2p 2p 2p
n = 1
l = 0 ,m = 0 n = 2 l = 0 ,m = 0
n = 2 ) l = 1
.(m = 1, 0, 1 ,
. , ?
, ? 2s 2p ,
,":

1s 2s 2p 2p 2p
87

 :6.3

, , .
,2s .2p
.
2s 2p ,
.

) 2s (25% ) 2p .(75%
2s 2p ,sp3 " "sp3
:

1s 2s 2p 2p 2p
1s sp3 sp3 sp3 sp3
,
.

6.6

V an der W aals

.

) (.
.
,H2 ) :(6.3
e2
p2 2
e2
p1 2

)+ W (r1 , r2 , R
2m
| |r1
2m
| |r2

=H

:
e2
e2
e2
e2
+

R
| |R + r2 r1 | |R + r2 | |R r1
.

88

= )W (r1 , r2 , R

 | |r1 |  |R |) |r2 |  |R,

( .
1
3
(1 + x)1/2 = 1 x + x2 + ...
2
8
:
#

)(r1 R) (r2 R
2

||R

"
r1 r2 3

e2
3

)W (r1 , r2 , R

||R

W . |n1 i
,|n2 i .|n1 n2 i
:
= h00|W |00i

)(1

E0

, :
2

)(6.8

||h00|W |n1 n2 i

E 0 E n1 n2

n1 n2 6=00

)(0

)(0

)(2

E0

R ,z :
e2
A
R6

)(2

E0

:
2

||h00|w|n1 n2 i

En1 n2 E0

n1 n2 6=00

)(0

)(0

=A

w = x1 x2 + y1 y2 2z1 z2
n1 = 0 n2 = 0:
h00|w|n1 0i = h00|w|0n2 i = 0
n1 > 0 ,n2 > 0
) 6.8 (Ry:
" #
#
1
1
1
1
2 +
2
2 +
2
)(n1 + 1
)(n2 + 1
)(0 + 1
)(0 + 1
:
3
)(0
)Ry En(0
E00 2Ry
1 n2
2
89

"
=

)(0

)En(0
E00
1 n2

)(0

)(0

,En1 n2 E00 = 2Ry = e2 /a0:

a0 X
2
||h00|w|n1 n2 i
e2 n n
1 2
a0 X
h00|w|n1 n2 ihn1 n2 |w|00i
e2 n n
1 2
a0
h00|w2 |00i
e2

A
=
=

1
h0|r2 |0i
3
Z
4
e2r/a0
r4
dr
3
4a30

= h0|x2 |0i
=

a20

:
h00|w2 |00i = 6a40
V an der W aals:
6e2 a50
R6

)(2

E0

:
6.47e2 a50
R6

)(2

E0

, .
.R  a0 , ,
) ( .
:
R
~
~ 2a0
= tlight  telectron
= 2
c
E0
e
.R  14nm ,
R .0.5  R  140
,
.1/R7

6.7

.1 ,
.
90

 .2 ,
Born Oppenheimer .
.3 H2+ H2 ,
.
.4 , "
) (
. "".
.5 V an der W alls ,
.
1/R6 .

91

7.1

, :
H = H0 + V
H0 V .H0
, V . :
)H = H0 + V (t
, t = 0 "" .V (0) = 0 ,
| (0) i .H0 ,
,t = 0 :
)(7.1

) (0
| , ti = H0 | (0) , ti
t

~i

, :
)(7.2

|, ti = [H0 + V (t)] |, ti
t

~i

:
|, 0i = | (0) , 0i
7.2 ) H0 ( ,
" ".
: |, tiS .
:
)(7.3

|, tiI eiH0 t/~ |, tiS

92

 ,t = 0 ,|, 0iI = |, 0iS .|, 0i

: QS .
:
~QI eiH0 t/~ QS eiH0 t/

)(7.4

. 7.3:
~ iH0 t/

e
|, tiS + eiH0 t/~ |, tiS
t
t
i

H0 eiH0 t/~ |, tiS + eiH0 t/~ |, tiS

~
t
i

H0 |, tiI + eiH0 t/~ |, tiS

~
t

|, tiI
t

=
=

~ i 7.2 .:
= H0 |, tiI + eiH0 t/~ [H0 + V (t)] |, tiS

|, tiI
t

~i

= H0 |, tiI + H0 eiH0 t/~ |, tiS + eiH0 t/~ V (t)eiH0 t/~ eiH0 t/~ |, tiS
|
{z
| }
{z
|}
{z
}
|,tiI

|,tiI

)VI (t

|, tiI = VI (t)|, tiI

t

~i

.
:
t

VI ( )|, iI d
0

1
~i

|, tiI = |, 0iI +

:
t

)(7.5

VI ( )|, 0id
0

7.2

1
~i

|, tiI |, 0i +

t = 0 |miS .H0 ,
, ,7.1 ,t > 0 :
|m, ti = eiH0 t/~ |m, 0i
, ) |ni ,H0 ,(n 6= m ),
( . ,
93

 . , t |ni
|mi . .
|m, 0i .H0
t:
|n, ti = eiH0 t/~ |n, 0i
) .V (t :
hn, 0|eiH0 t/~ |m, ti
hn, 0|m, tiI

= hn, t|m, ti
=

7.5
t

VI ( )|m, 0id
0

1
~i

|m, tiI = |m, 0i +

| hn, 0:
1 t
hn, 0|V I ( )|m, 0id
i~ 0
Z t
1
hn, 0|eiH0 /~ V ( )eiH0 /~ |m, 0id
mn +
i~ 0
Z
~1 t i(En Em ) /
mn +
e
hn, 0|V ( )|m, 0id
i~ 0
Z

mn +

hn, 0|m, tiI

=
=

m
|m, 0i = |mi , En E ,|n, 0i = |ni
mn
~

|m, 0i |n, ti ) ,(n 6= m ,t:

 Z t
2
1

2
imn

 = |Pmn (t) |hn, t|m, ti
)(7.6
e
 hn|V ( )|mid
~ 0
.

7.3

F ermi

,t = 0 ,H0 t = 0 V
) .(V
|m, 0i |n.ti ?t ,7.6:
Z t
2

1
 2
imn

= )Pmn (t
|hn|V
||mi
e
d


2
~
0
 i t
2
mn
1
 1
2 e
=
 ||hn|V |mi
2
~
 mn

2
1
)2 sin(mn t/2
||hn|V |mi
=
~2
mn /2
94

 :7.1 )t (

,
) :(7.1
)sin2 (t
2 t
) F (
Z
lim
)t ()F ()d = F (0
= )t (

:
)lim t () = (

, t :


En Em
1
2
|hn|V |mi| t
)Pmn (t
~2
~2
2
2
=
|t (En Em ) |hn|V |mi
)(7.7
~
) ,(En = Em
, V
.
7.7 :
)Pmn (t
2
2
=
| (En Em ) |hn|V |mi
t
~
) ( "" ,
mn

:
Z
mn (En )dEn

mn

X
n

95

 :7.2 .F ermi

(En )dEn En .En + dEn

. :
)(7.8

2
2
|(Em ) |hn|V |mi
~

= mn

X
n

" " ) " (.

. 7.5 , 7.7 ,
. ,
.
]~ .t [(En Em )/2 t ,
) 4~/t .(7.2 ,
) E (7.2
.
.
, ) E (7.2 .
" :
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 E
t

 E

:
h
h
t
E
E
, 7.5 , ,
.1 :
h
2

||mi

4 2 (Em ) |hn|V

96

t

 :7.3 ) t (.

7.4

V ,t = 0
:
0

t<0
it

+F e

t>0

it

Fe

(
= )V (t

)" .(107 egap no

7.6:
t

ei(mn +) hn|F |mid

)(7.9

Z
0

1
~

ei(mn ) hn|F |mid +

Z
0

1
~

= hn, t|m, ti

, .
) .t ( 7.9 ,
) .(7.3:

2

2
2



(En Em ~) |hn|F |mi| + (En Em + ~) hn|F |mi
=
~


mn

)(7.10

, .|En Em | = ~

7.5

.1 H0
, ) ,,
, (.
.2 ) ~( " "
.
.3 F ermi ) (t = 0
.
. .
97

 .4 ,
~.

98

8.1

8.1.1

) (

:
)(8.1

B=0

E = 4
)(8.2
1 E 4
+
J
)(8.3
=B
c t
c
1 B
=E
)(8.4
c t
:

=0
)(8.5
t
:

J+

B = A
)(8.6
1 A

)(8.7
E =
c t
8.6 8.7 8.1 8.4 . 8.2 8.3
:
)(8.8

)(8.9

1
1 2 A 4

2 2 +
J
c t
c t
c
99

1
)( A
c t

= ( A) 2 A

 , .
, A
= A +
1
=
c t

8.1.1.1

A0
0

) (r:
1 2
1
=A+
2
2
c t
c t

2 +

8.8 8.9:
)(8.10

)(8.11

)(8.12

4
J
c

1
c t

A+

1 2
2
c2 t2
1 2A
2 A
c2 t2

8.11 8.12 .
,
.
.8.10
8.1.1.2

A=0
:
)(8.13
)(8.14

= 4
4
1
=
J
c
c t

1 A
2 A
c2 t2

8.13 , 8.13 8.14

.
8.13 :
(r0 , t) 3 0
d r
| |r r0

100

= )(r, t

8.1.2

"" , . = J = 0 8.14 ,
:
2

1 A
= 2 A
c2 t2

)(8.15

,
.
) ""( :
A (r)eick t
) A (r . , )
( , ) k ( ,
:A
2 A + k2 A = 0

)(8.16

{A } )
( , A :
X
= )A(r, t
)q (t)A (r
)(8.17

A A d3 r = 4c2

:
A(r, t)A (r)d3 r

1
4c2

= )q (t

:
q (t) = Q ei t
. ck

8.1.3

) A A (.
8.17 ,8.14 , A
. :
X
= )J(r, t
))ej r j (t) 3 (r rj (t
j

101

 ej .rj
:q
t)d3 r
A (r) (r,

4 X
1
1
= q + k2 q
ej r j A (rj )
2
c
c j
c

t)d3 r 0 :
A (r) (r,

4c2

,L L

.
: , A = 0 :
Z
Z


= 3r
A d
A d3 r
I
dS
=
A
L3/2
.

:
) r j A (rj

X ej
c

= q + 2 q

8.1.4

m q :
q
mr = qE + v B
c
:
 1
q 2
=H
p A + q
2m
c

) ( , ) (.
.
.1 : mi qi
:

X 1
qi 2 X
=H
pi A +
qi
2mi
c
i
i

102

 .2
(ri ) i" :
X
qj
=
| |ri rj
j6=i

ei ,qi :
 X 1
ei 2 X X ei ej
=H
pi A +
2mi
c
| |ri rj
i
i j<i

.3 8.17 A :
!2
X 1
X X ei ej
ei X
=H
pi
q (t)A (r) +
2mi
c
| |ri rj
i
i j<i

.4 :
. ,


P
, 21 p2 + 2 q2 q
8.17 "" , p . :
!2
X 1
X X ei ej


ei X
1X 2
=H
pi
+
q (t)A (ri ) +
p + 2 q2
2m
c
|r

r
|
2
i
i
j

i
i j<i
.

) (.

8.2

, " .
)
.(~ ,
:
q + ip
p
2~
q ip
p
2~

:
[a , a ] =
103

 a ) ,( a
) .(
,


X
1
=H
~ a a +
2

:
)q (t)A (r

)A(r, t

s


~
)a (t) + a (t) A (r
2

)(8.18

:
a (t) = a (t = 0)ei t

8.2.1

) A(r, t

.V = Lx Ly Lz ) A (r
:
r

8c2
sin(k r)k
V
r
8c2
=
cos(k r)k
V
=

)A(s)k (r
)A(c)k (r

k = 1, 2) .(k
k , ,kz > 0:
2nx
Lx
2ny
Ly
2nz
Lz

kx

ky

kz

nx , ny , nz . 8.18 ,
~ 8c2

2 V




i
a(s)k (t) + a(s)k (t) sin(k r) + a(c)k (t) + a(c)k (t) cos(k r) k
104

X
k

h

)A(r, t

:
ak

ak

a(c)k ia(s)k

2
a(c)k + ia(s)k

2
:

[ak , ak0 0 ] = kk0 0

:kz < 0 kz > 0 A(r, t)  k = k
s
i
X 2~c h
(8.19)
ak eikrik t + ak eikr+ik t k
A(r, t) =
V |k|
k

8.2.1.1

: , ,z k
(
( = 1)
x
k =
( = 2)
y
:
k =

i
x
y

2
:

ak =

ak1 iak2

2
:

s
A(r, t) =

X
k=

i
2~c h
k ak eikrik t + k ak eikr+ik t
V |k|

(8.20)

:
[ak , ak0 ]

kk0

[ak , ak0 ]

[ak , ak0 ]

[ak , ak0 ]

105

8.3

8.3.1

:


X
1

~k ak ak +
2
k

) (
:


X
 1
e 2
1
p A + e +
~k ak ak +
2me
c
2

, A = 0 , .[p, A] = 0
2e
e 2
e2
p A = p2 p A + 2 A2
c
c
c

" " ""

:

)H = H0 + V (t
:



X
p2
1
+ e +
~k ak ak +
2me
2
k
e
e
=
p A(r, t) +
)A2 (r, t
me c
2me c2

H0
)V (t

H0 , .
,|ni , .|n i
" .|n, n i
) V (t , A .A 8.19
A ,
A .
""
.
|mi |ni
) k  ,
106

 ( . , |m, n i
.|n, n + 1i
8.20 :
s
2~c ikr+i t
= )A(r, t
 a e
V |k|

, , , 7.10 :
2
2
| (En + ~ Em ) |hn, n + 1|F |m, n i
~

= m n

:
2~c
p  a eik r
V |k|

e
me c

F =

:
s

2~c
e
hn, n + 1| a
p  eik r |m, n i
|V |k
me c
s
)2~e2 (n + 1
hn|p  eik r |mi
=
V |k| m2e c2

= hn, n + 1|F |m, n i

2

2
)(2e) (n + 1
 (En + ~ Em ) hn|p  eik r |mi
2
V |k| me c

= m,n n,n +1

, ,n = 0 "
" .
) 0 ( . 0 ,
)( .
.d
~ = ~c |k| ) m,0n,1
,(n = 0 ) :(|k | = k
Z
V
2
=
3 ~ckm,0n,1 k dk
)(2
 
 2 e2
 hn|p  eik r |mi2
=
2m2e c3
~ =(Em En )/

107

dP
d

8.3.2

eik r :
ka0
a0
=
c

a0
~c
e2 a 0
2a0 ~c
e2
2~c

2
1
1
274

k r

=
=

:
eik r 1
" " . :
hn|p  eik r |mi

hn|p  |mi
p
|= me hn
|mi
me
i
= me hn|[H0 , r]|mi
~
i
= me (En Em ) hn|r|mi
~

:
dmn = hn|r|mi
) " "(
:
2
 4 e2
 dmn 
3
2c

dP
d

~. = (Em En )/

:
)(8.21

4 4 e2
2
| |dmn
3c3

108

= Pmn

8.3.3

) (,
:
dk

3 m,0n,1 k

)(2

dW
=
d

, .~ :
2
dW
1 dP
 3 e2
 dmn 
=
=
3
d
~ d
~ 2c
:
4 3 e2
2
| |dmn
~ 3c3

= Wmn

dmn ,n .
|mi .
|mi ,m :
X
1
=
Wmn
m
n

. ,
.
2

. |dmn | a20:
1
4 3 e2 a20
8 E0
3

) (ka0

~ 3c3
~ 3
= 1000:
0.5 nsec

8.3.4

. ,
.dmn ,
W igner Eckart .

,dmn = hn|r|mi r )) r(1 .(2.18,

. |mi |ni
" , . ,
109

 |initi ,|mi |f inali .|ni

.dif = hf inal|r|initi |initi |f inali
, W igner Eckart :
)(8.22

dif = h0 , J 0 , M 0 |rq(1) |, J, M i h1, J, q, M |J 0 , M 0 i

.q = 1, 0, 1 dif :
)(8.23

= M 1, M, M + 1

M0

, k = 1 , :
)(8.24

|J 1| J 0 J + 1
)(1

i riq
)(1
riq

)(1

( .

) rq i

,Li S Lj ) i 6= j
" .(25 ),
' ( . , p
":
)(1

riq |n1 , l1 , ..., np , lp , L, S, J, M i

| dif = hn1 , l1 , ...n0p , lp0 , L0 , S 0 , J 0 , M 0

,
.
.
: :
.1 .S
.2 ) J = 1, 0, 1
J = 0 J 0 = 0(.
.3 ) L = 1, 0, 1
L = 0 L0 = 0(.
.4 M .M = 1, 0, 1
.5 lj = 0
.li = 1, 1
.6 nj = 0 )
( ni .

110

 : , ,
.
: 5 , l = 0 .
:
)(1

)(1

.1 riq ,S hS 0 |riq |Si

.S = S 0
.2 .8.24
.3 1 2".
.4 .8.23
)(1

.5 riq Lj ,i 6= j
) lj .(1 ,Li
li 0 .1 li :0
lj , .li d
1 ,2 )
li ( .
Z
= 1 r2 d3 r
)(8.25

d12

1 2 .Ylm
Ylm ,(1)l lj ,
. 1 2 . r ,
8.25 . , lj .
.6 ,5 nj
.

8.3.4.1

: Zeeman

8.1 Zeeman )
Zeeman " (77 .
,J = 3/2 ,S = 3/2 ,L = 1 ,S 0 = 3/2 ,L0 = 2
.J 0 = 5/2 L = 1 ,S = 0 .J = 1
M ) M = 1, 0, 1
.(8.1

111

 :8.1 Zeeman

:
E = B BgLSJ M
5.19 gLSJ . :
26
15

= gLSJ

:
48
35

= gL0 S 0 J 0

,gLSJ > gL0 S 0 J 0 B B ,

) 8.1
( . , 8.1
. , .
8.21 :
4 4 e2
2
| |dmn
3c3
8.22 dmn :CG
h1, J, q, M |J 0 , M 0 i
12 . ,
CG.

112

8.3.5

. ,
,
, )( .
, .
, ,
.
H0 ) H = H0 + V
( ,n |(t)i
, , V
o
)(0
: | (t)i

a (t)|(0) (t)i

= |(t)i

, .
H0 :
|(0) (t = 0)i

~t/

)(0

|(0) (t)i = eiE

:
|(0) (t = 0)i

~t/

)(0

a (t)eiE

= |(t)i

|(t)i = (H0 + V ) |(t)i

t

~i

:




X
)(0
)(0
a
= + E(0) a eiE t/~ |(0) (0)i
a eiE t/~ E(0) + V |(0) (0)i
t

)(0

~i

X

|) h (0 ):a (t
~a (t) X i(E(0) E(0) )t/
=
e
)V a (t
t

:
V = h(0) (0)|V |(0) (0)i
.V = 0 :
(
)1 ( = 1
= )a (t = 0
)0 ( 6= 1
113

~i

 |) |a (t)|  |a1 (t 6= 1 .t > 0

= 1 :
)(8.26

V1



)(0
)(0
~t/
i E
E1

)a (t
a1 (t)e
t

~i

) a1 (t :
a1 (t) = eiE1 t/~1 t/2
1 E1 . 8.26 , 6= 1 :


)(0
)(0
i E1 +E1 E
t/~1 t/2

1e


)(0
)(0
E1 + E1 E + i~1 /2

a (t) V1

= 1 :


)(0
)(0



t/~1 t/2
i E1 +E1 E
X
)(0
)(0
~i
t/~ 1 e
2 i E1 E
iE1 t/~1 t/2


|V1 | e
E1 1 e

)(0
)(0
2
E + E E + i~ /2

6=1

) ,(:
) E(0) En(0

)(0

)~1n E1 + E1 En(0
x 1n
:
eitx+1 t/2 1
dx
x + i1 /2

)|V1 | (1n + x

XZ

1
~i
= 1
2
~

E1
2

,1  x  1n ) (1n + x) (1n | |V1

. :
itx

e
dx = 2ie1 t/2
x + i1 /2

1  1n:
Z
)(1n + x
)(1n + x
dx P.V.
) dx i(1n
x + i1 /2
x

, ~ ,E (E1n ) (1n )/ x0 = x ,:
2 X
2
) |V1 | E (E1n
~ n
Z
0
X
) 2 E (E1n ~x
=
P.V.
| |V1
dx0
0
x

n
=

114

1
E1

 1 , E1
.
1 t  1:
2

|V1 | /~2

( 1n ) + 1 /4

|)|a (t

. 6= 1
= 1:
)(0

)t/~ (0
|1 (0)i


)(0
i E1 +E1 t/~1 t/2

a1 (t)eiE1

)(0

|1 (0)i

)(0

|1 (t)i

,
! , ) H
( . ,|Ei ,
:
Z

)(0

hE|1 i |EidE

)(0

= |1 i

:t = 0
)(0

|1 i = |1i
:
)(0

|1 (t)i = |1, ti = eiHt/~ |1i

:
Z
hE|1, ti h1|EidE
hE|eiHt/~ |1i h1|EidE

= h1|1, ti
Z
=

:
2

eiEt/~ |h1|Ei| dE

)(8.27

Z
= h1|1, ti

| |h1|Ei E ,|1i
"" . 8.27
:
eiEt/~ h1|1, tidt

115

1
h

= ||h1|Ei

E
| E|1 |2

E1
E
2

:8.2 | |hE|1i ) |1i(

:
a (t)|, ti

= h1|1, ti

|h1

|i

~t/

)(0

a (t)eiE

|h1

h1|i

~t/

)(0

a (t)eiE

~t/

)(0

a1 (t)eE1

)(0

E1 = E1 + E1:
)~1 /(2
2

)(E E1 ) + (~1 /2

= ||hE|1i

) 1 ,(8.2 .E = ~1
.1 1/

8.3.6

,n
) .(n n 1
1

/2
1
(xx0 )2 +(/2)2

= )L(x

116

: A(r) =
H=

q A (r)

.0

X


p2
1X 2
e
e
+ (r) +
p + 2 q2
p
q A (r)
p q A (r)
2m
2
mc
mc
|
{z
}
6=
|
{z
}
V
H00

{z

H0

:( H00 ) t | i | i
 Z t
2
1

2
h|VI (t0 )|idt0 
P (t) = |h|, tiI | = 
~ 0
:
h|VI (t)|i =
=

h|eiH0 t/~ V eiH0 t/~ |i

X
h|eiH0 t/~ |ih|V |ih|eiH0 t/~ |i
,

,H00 | i | i
: = , =
h|VI (t)|i

h|eiH0 t/~ |ih|V |ih|eiH0 t/~ |i


 

eiE t/~ t/2
eiE t/~ t/2 h|V |i

= ei(E E )t/~( + )t/2 h|V |i

:~ = E E
P (t)

=
=

 Z t
2
1
[i 12 ( + )]t0 h|V |idt0 

e
~

0


1
2
1  e[i 2 ( + )]t 1

h|V |i

i
2


~
+ 2 ( + )
1
2
|h|V |i| t ( , + )
~2
:

t (, )



 e[i 12 ]t 1 2


= 

 + 2i 
=

4sin2 (t/2) et/2 + 1 et/2

2 + 41 2
(
2t() (t  2  t)
1
2 + 14 2

117

(t  1)

2

 t  2  t ,F ermi
t  1 :
1
2

) ( +

1
4

1
2
||h|V |i
2 +
~2

) P (t

)2 |h|V |i| ( + ) / (2
2 + 1 ( + )2
~2 +

4
{z
}
|

Lorentzian

) ( |mi ,|ni
. :
)2~e2 (n + 1
2
||hn|p e |mi
| m2 cV |k
2~e2 n
2
||hn|p e |mi
| m2 cV |k
2~e2
2
+ 2
||hn|p e |mi
| m cV |k

)(8.28
)(8.29

||hn, n + 1|V |m, n i

8.29 , 8.28
. :
2

 2
hn|p e eik r |mi
2e
)( + ) / (2
= ) P (t
u
2
2
m~
+
) ( mn ) + 1 ( +
4

n
V

u = ~

) .(
) = mn (
2

) ,( + .

) (,
, .

8.4

.1 .
.
.2
) (.
.3 .
118

 .4 ,
.
.5 .

119

9.1

. , )
,(9.1 ) ( ,
. ) ,
,( ) d , ( ,
.
.
:
, .
)
( .
dsc
d

: ,
. ,
:
Z
dsc
= sc
d
d
:
d
sindd
d
120

Z
=

 :9.1

: .
,
.

9.2

, p = ~k ,p2 /2m
. , )V (r
. k in
:sc
k (r) = eikr + sc
:
 2 2

~

)+ V (r) k (r) = Ek (r
2m
E = ~2 k 2 /2m:


2m
)2 + k 2 k (r) = 2 V (r)k (r
~
) G(r r0 :


) 2 + k 2 G(r r0 ) = 3 (r r0
) sc
(.
121

:
0

| eik|rr
G(r r ) =
| 4 |r r0
0

:
Z

)(0

)V (r0 )k (r0 )G(r r0 )d3 r0 + k (r

2m
~2

= )k (r

)(0

k (r) = eiki r :
)
(0
2 + k 2 k (r) = 0
) V (r , , |,|r0 |  |r
:
0

r r
= |r| n r0
||r

|r r0 | |r|

n .r
:
eikr ikf r0
e
4r

) G(r r0

.kf = kn :
eikr
r

)(9.1

) k (r) eiki r + f (r

:
0

V (r0 )k (r0 )eikf r d3 r0

m
2~2

f (r ) =

" " . 9.1 eiki r

ikr

,f (r ) e r ,r " ) .f (r

) f (r .k
) f (r ...k , .
, ? ,
. :
~

)Im(
m

=J

, )
( . :
~ki
m

= Ji

122

 :
2

|) ~kf |f (r
m
r2

Jf

:
Jf dS
dS .Jf :
Jf dS
| |Ji
) ( .
:
|Jf | r2 d
| |Ji
:
dsc
2
|)= |f (
d
:
Z

|f ()| d

9.3

= sc

, .
, .
, :
~

) Im(k k
m

 

~
eikr
eikr
iki r

iki r
Im
e
) + f (r
iki e
) + ikf f (r
m
r
r

)(9.2
)(9.3

~ki
|) ~kf |f (r
+
m
m
r2


~
ikriki r
+
Im ikf e
) f (r ) + iki eikr+iki r f (r
mr

9.2 9.3 .
123

 : .
: k ) ( .
. J = 0
:
I

Z
( J)dV = 0

= Jd
V


:
I
Jd
I
2
|) ~kf |f (r
~ki
d +
d
m
m
r2
I


~
ikriki r
+
Im ikf e
f (r ) + iki eikr+iki r f (r ) d
mr

i
~k , . :
m
I
I


2
kf |f (r )| d = rIm ikf eikriki r f (r ) + iki eikr+iki r f (r ) d

) kf
I


rIm ikf eikriki r f (r ) + iki nf eikr+iki r f (r ) d
I


r Im ieikriki r f (r ) + ini nf eikr+iki r f (r ) d
I
r
]) [1 + (ni nf
)(9.4

2
 ikriki r

e
f (r ) + eikr+iki r f (r ) d
)(9.5

.(nf :
I
2
= kf |f (r )| d
I
2
= |f (r )| d
I
2
= |f (r )| d

| .|ki | = |kf
9.4 9.5 )
( . u = cos ki .kfni nf = u ,
:
1



(1 + u) eikriki r f (, ) + eikr+iki r f (, ) du

Z
d

u r:
[ if (, )|u=1 if (, )|u=1 ] d
124

1
k

sc =

r
2

sc =

 ,u = 1 , = 0 , :
2
])[if ( = 0) if ( = 0
k

sc =

:
4
])Im [f ( = 0
k

= sc

.
:
) ( : sc abs
. , tot = sc + abs:
4
])Im [f ( = 0
k

= tot

: :
Jd
= abs
| |Ji

.

, .

9.4

Born

.k ) ,f (r
) f (r :k
0

V (r0 )k (r0 )eikf r d3 r0

m
2~2

f (r ) =

) k (r0 ,eiki r:
Z
0
m
V (r0 )ei(kf ki )r d3 r0
f (r ) =
2~2
1 k = kf ki ):V (r
Z
V (k) = V (r)eikr d3 r
1 ,k = 2ksin 2k | k = |k0 | = |k k k .k0
125

 :
m
)V (k
2~2

f (r ) =

:
2
  m 2
dsc


=
)V (k
2
d
~2
:
)sc (r = 0)  i (r = 0
:

sc (r = 0)  eiki r r=0 = 1
:
.1 : a V0 , :
~2
ma2

 V0

.2 : |ki | = k ,ka  1 :
r
~2
~2
 V0
ka

E
ma2
ma2

9.5

b
) a .(9.2 , ,b a
:
L = |r p| = bp ap
:
L ~ka
L2
2
) (ka
~2
2
)l(l + 1) (ka
126

 :9.2 .
.

,ka  1 , .l = 0 ,
in = eiki r ,L2 l = 0
) (.
, :
l
X
X

)clm (k)jl (kr)Ylm (,

= eikr

l=0 m=l

,k = k ,
) jl (kr . z
:m = 0
)Al jl (kr)Yl0 (,
)Al jl (kr)Pl (cos

X
l=0

eikrcos

=
=

l=0

' :
1

Pl (z)eikrz dz
"

1p
)4 (2l + 1
2

1p
)4 (2l + 1
2

#
l+1
l
)(ikrz
)(ikrz
+
+ ... dz
Pl (z) 1 + ikrz + ... +
!l
!)(l + 1
1
1

ka  1 |r|  a:
l

1p
!(ikr) 2l+1 l
)4 (2l + 1
2
!)(2l + 1

)Al jl (kr

:
!2l l
l
)(kr
!)(2l + 1

= )jl (kr

:
p
)4 (2l + 1
127

Al = i l

=
=

)Al jl (kr

 :
)il (2l + 1) jl (kr)Pl (cos

= eikrcos

l=0

, ":
0

| eik|rr
V (r0 )k (r0 )d3 r0
| 4 |r r0
1
V (r0 )k (r0 )d3 r0
| 4 |r r0
Z

2m
~2
Z

= eiki r
2m
~2

)k (r

,k :
)k (r) k=0 (r
:
V (r0 )k=0 (r0 )d3 r0 = const

m
2~2

f (r )

. :
f (r ) a0 ei0
:
= a20
4a20

dsc
d
sc

:
4
])Im [f ( = 0
k
4
= a0 sin0
k
=

sc

:
sin0 = ka0

) f ( ,a0 " " . 0 "

."l = 0

9.6

F ermi

eiki r

1
V

= ,|ii eikf r

1
V

= |f i )) V (r

.(V
128

 .
:
2

2


=
(Ei Ef ) hf |V |ii
~

Wif

:
2

2
V


(Ei Ef ) hf |V |ii d3 kf
3
~
)(2
 Z
2


2 V
2 dkf  1
ikf r
 iki r 3
kf
e
V (r)e
d r

3
)~ (2
dEf V
Z

Wki kf

k = kf ki ):V (r
Z
V (k) = V (r)eikr d3 r

:
2
kf2
 dkf

V
)(k


(2)2 ~V dEf
2
kf2
 m

V
)(k


(2)2 ~V ~2 kf

Wki kf

":
Wki kf
) d(ki kf
=
dkf
| |Jki
:
~ki
mV

= Jk i

:
2

dsc
 m 2

V
)(k
=


d
2~2
.Born

9.7

.1 .
.2
. .
.3 , " /"
.
129

 .4 ) (
) .(0
.5 Born .
.
.6 , L2
l = 0 . .
.7 .F ermi
.Born

130

 10

10.1

:
~p = i
" ":

~E = i

:
p2
2m

=E

~2 2
=

t
2m

~i

:
E 2 = m2 c4 + p2 c2
, :

2  2 4
= m c c2 ~2 2
2
t

131

 .Klein Gordon

. , .
:
|E = |pc
, :

|| = 2
.
:
)(10.1

E = ( p) c

. .
,
) ~ (k = p/
.p ,k :
E = ~ |k| c
, , .
.
,
. ) ( ,
. ,
.
.10.1
) " "( ,
)" "( .
,0 .
" ,
. " "
" " . ,
!
H
0
H

) , H (2 2

d
132

 ) a (b ,H
) c (d .H . ,
, " ".
a, b ,c, d
" " :

10.2

0
K
1

3 ,2 ,1 2 2 .:
!
1 0
= 3
0 1
,:
!

= 3

) (

0
0 1 0

0
0
0 1

1 0
0
0

0 1 0
0
. :
H = ( p) c + K
,K :
E|i
0

= H|i
= [( p) c + K E] |i

[( p) c + K + E] [( p) c + K E] |i = 0
 2 2

p c + K 2 E 2 |i = 0
:
K = mc2
133

 :


( p) c + mc2 |i = E|i

: A B . :
{A, B} AB + BA

H = ( p) c + mc2 .
z ,y ,x ) 4 4 .(
" " .:
1

2ij

} {i , j

}{i ,

) (i

:
)(a

)n (r, t)nk k (r, t

4
X

(r, t) c

)(a

n,k=1

) (a ) 2 ,1 (3 J .
:
P
+J=0
t

10.3

, .
"
":
!

0
=
0

134

) ( . :
!

, .
:
)H = [ (pc eA(r))] + mc2 + e(r
, = p ec A :
!
!
!

2
+ e
+ mc

!
=c

:
!
)(10.2

!
+ e

!

E mc2


=c
E + mc2

E mc2 10.2:

)(10.3

2mc2 = c + e

e
=
+

2mc
2mc2

, :
Ek v 2
10.3 ,v 2 /c2 .
,v/c .|| v:

2mc

10.2:



1
2
= E mc
( ) ( ) + e
2m


)(




 1
e 2
~e
= E mc2
p A
( B) + e
)(10.4
2m
c
2mc
:
)( ) ( ) = 2 + i (

135


. , x :
( )x = y z z y
, .
:
1
)(B r
2

=A

:
)= p (B r

2p A

)= B (r p
= BL
10.4 ,



~e
e2
p2
2

(L + 2S) B + e +
A

= E mc2
2m 2mc
2mc2


, 2 .g ,
.g = 2 v/c
,g :

p2
p4
~e
e~2
2
= 
+ e

(E v) +

2m
8m3 c2
4mc2
8m2 c2


: ,
) ,(T homas
.Darwin " ".

10.4

.1 .
.2
.
. "".
.3
.
.4
. , g .

136


, "M adKat , , '
:
Schwabl F. (2002), Quantum M echanics (3rd. ed.), Springer
Sakurai J.J. (1994), M odern Quantum M echanics (rev. ed.), Addison
W esley
Shankar R. (1994), P rinciples of Quantum M echanics (2nd. ed.), P lenum
Gasiorowicz S. (1996), Quantum P hysics (2nd. ed.), W iley
W ikipedia : Angular M omentum Coupling
W ikipedia : Electron Conf iguration
W ikipedia : T erm Symbol
W ikipedia : List of Hund0 s Rules
W ikipedia : Orbital Hybridisation
W ikipedia : Distribution (mathematics)
W ikipedia : F unctional Derivative
W ikipedia : Lagrange M ultipliers
W ikipedia : W EIZAC
137

F ox A.M., Atomic and Laser P hysics (Lecture N otes), U niversity of Shef f ield
(http : //www.mark f ox.staf f.shef.ac.uk/P HY 332)
Spherical T ensor Operators

(http : //atoms.vuse.vanderbilt.edu/
Elements/CompM eth/HF/node30.html)

Hybridization T heory

(http : //www.bcpl.net/ kdrews/

hybridization/hybrids.html)

138


:Bohr
B =

e~
2me c

:
L2 |lmi = ~2 l(l + 1)|lmi

Lz |lmi = ~m|lmi
[Ji , Jj ] = iijk ~Jk

:W E
h 0 j 0 m0 |Tq(k) | jmi =

1
h 0 j 0 ||T(k) || jihkjqm|j 0 m0 i
2j 0 + 1

:
hj, m0 |Vq(1) |j, mi =

hj, m|J V|j, mi

hj, m0 |Jq(1) |j, mi
~2 j(j + 1)

:
En(1) = hn(0) |V |n(0) i

En(1) =

1
(Z)4

2
2me c
n3
139

:

1
3

4n
l + 12

 :
(


l
j = l + 12
g
1
2
4


= me c (Z) 3

4
)n l(l + 1)(2l + 1
l 1
j = l 12

:Zeeman
E = B BgLSJ M

:Land
e
)J(J + 1) + S(S + 1) L(L + 1
)(ge 1
)2J(J + 1

gLSJ = 1 +

:t0
Z
1 t
VI ( )|, 0id
|, tiI |, 0i +
i~ t0

:
 Z t
2
1

 = )Pmn (t
 eimn hn|V ( )|mid
~ 0

":
q + ip
p
2~
q ip
p
2~

) (:
4 3 e2
2
| |dmn
~ 3c3

= Wmn

) (:
4 4 e2
2
| |dmn
3c3
140

mn

)En(1

 :
dsc
2
|)= |f (
d

:Born
V (r)eikr d3 r

m
2~2

f (r ) =

:
4
])Im [f ( = 0
k

141

= tot


.1 .
.2 .m
.3 .
.4 .
.5 .
.6 , .
.7 .
.8 .
.9 " +" .
.10 " .
.11"" .
.12 .
.13 : .I
.14 : .

142

32. Clebsch-Gordan coefficients

32. CLEBSCH-GORDAN COEFFICIENTS, SPHERICAL HARMONICS,

AND d FUNCTIONS
p
Note: A square-root sign is to be understood over every coefficient, e.g., for 8/15 read 8/15.
r

1
0
+1
1
0
0
+ 1/2 + 1/2 1
+ 1/2 1/2 1/2 1/2 1
1/2 + 1/2 1/2 1/2 1

1/2 1/2

1 1/2

3/2
+ 3/2 3/2 1/2
1 + 1/2 + 1/2
+ 1 + 1/2
1/3 2/3 3/2 1/2
2/3 1/3 1/2 1/2
0 1/2
1 + 1/2

m1

...
...

m2

3
cos
m 1 m 2 Coefficients
21/2 + 5/2
4
5/2 5/2 3/2
.
.
r
1 3/2 + 3/2
+ 2 1/2
.
.
3
1
i
Y1 =
sin e
.
.
+ 2 1/2 1/5 4/5 5/2 3/2
8
+ 1 + 1/2 4/5 1/5 + 1/2 + 1/2
r 

5 3
1
+ 1 1/2 2/5 3/5 5/2 3/2
Y20 =
cos2
0 + 1/2 3/5 2/5 1/2 1/2
4 2
2
r
0 1/2 3/5 2/5 5/2 3/2
15
1 + 1/2 2/5 3/5 3/2 3/2
Y21 =
sin cos ei
2
8
1 1/2 4/5 1/5 5/2
3/21/2 + 2 2 1
r
2 + 1/2 1/5 4/5 5/2
1 15
2
2
2i
+1/2
1
+
3/2
+
1
+
1
Y2 =
sin e
2 1/2
1
4 2
1
+ 3/2 1/2 1/4 3/4 2

Y10 =

1/2 1/2 1

+ 1 1/2
0 + 1/2

Notation:

2/3 1/3 3/2

1/3 2/3 3/2

0
+ 1/2 + 1/2 3/4 1/4 0
3
1 1/2
1
1
+ 1/2 1/2 1/2 1/2
3/21 + 5/2
2
+3 3
2
5/2 5/2 3/2
1/2 + 1/2 1/2 1/2 1 1
+2 +1 1 +2 +2
+ 3/2 + 1
1 + 3/2 + 3/2
2
+ 2 0 1/3 2/3
1
3
1/2 1/2 3/4 1/4 2
3/2 1/2
+ 3/2 0 2/5 3/5 5/2
+ 1 + 1 2/3 1/3
+1
+1
+1
3/2 + 1/2 1/4 3/4 2
+ 1/2 + 1 3/5 2/5 + 1/2 + 1/2 + 1/2
+ 2 1 1/15 1/3 3/5
3/2 1/2 1
2/5 1/2
+ 3/2 1 1/10
2
2
1
1/6 3/10
3
+ 1/2 0 3/5 1/15 1/3 5/2
3/2 1/2
1 1 + 2 2 1 + 10 + 01 8/15
6/15 1/2 1/10
0
0
0
1/2 + 1 3/10 8/15 1/6 1/2 1/2 1/2
+1 +1 1 +1 +1
+ 1 1 1/5 1/2 3/10
+ 1/2 1 3/10 8/15 1/6
0
+ 1 0 1/2 1/2
2
1
2
1
0 2/5
0 0 3/5
3
1/2 0 3/5 1/15 1/3 5/2 3/2
0 + 1 1/2 1/2
0
0
0
1 + 1 1/5 1/2 3/10
1 1
1
3/2 + 1 1/10 2/5 1/2 3/2 3/2
1/2 1 3/5 2/5 5/2
0 1 6/15 1/2 1/10
+ 1 1 1/6 1/2 1/3
3/2 0 2/5 3/5 5/2
2
1 0 8/15 1/6 3/10
3
0 1/3 2
0 0 2/3
1
2 + 1 1/15 1/3 3/5 2 2
1 + 1 1/6 1/2 1/3 1 1
3/2 1
1
1 1 2/3 1/3 3
0 1 1/2 1/2 2
m
m
m
hj1 j2 m1 m2 |j1 j2 JM i
Y`
= (1) Y`
2 0 1/3 2/3 3
r
1 0 1/2 1/2 2
4
1 1 1
= (1)Jj1 j2 hj2 j1 m2 m1 |j2 j1 JM i
d `m,0 =
Y`m eim 2 1 1

21

2` + 1

j
d m0 ,m

0 j
(1)mm d m,m0

j
d m,m0

1 + cos
1/2
+3 3
d 10,0 = cos
d 1/2,1/2 = cos
d 11,1 =
2
2
2
+ 3/2 + 3/2
1 +2
+2

sin
1/2
2 3/2 + 7/2
3
2
1
+ 3/2 + 1/2 1/2 1/2
1
d 1/2,1/2 = sin
d 1,0 =
7/2 7/2 5/2
+ 1/2 + 3/2 1/2 1/2 + 1 + 1
+1
2
2
+ 2 + 3/2
1 + 5/2 + 5/2
+ 3/2 1/2 1/5 1/2 3/10
1 cos
5/2 3/2
+ 2 + 1/2 3/7 4/7 7/2
1
0
3
2
1
+ 1/2 + 1/2 3/5
0 2/5
d 1,1 =
+ 1 + 3/2 4/7 3/7 + 3/2 + 3/2 + 3/2
0
0
0
1/2 + 3/2 1/5 1/2 3/10
0
2
+ 2 1/2 1/7 16/35 2/5
+ 3/2 3/2 1/20 1/4 9/20 1/4
5/2 3/2
1/2
+ 1 1/2 4/7 1/35 2/5
7/2
+ 1/2 1/2 9/20 1/4 1/20 1/4
0 3/2 2/7 18/35 1/5 + 1/2 + 1/2 + 1/2 + 1/2
1
3
2
2 2 44 4 3
1/2 + 1/2 9/20 1/4 1/20 1/4
1
3/2 + 3/2 1/20 1/4 9/20 1/4 1 1
+ 2 3/2 1/35 6/35 2/5
2/5
+2 +2 1 +3 +3
0 3/10
+ 1 1/2 12/35 5/14
+ 1/2 3/2 1/5 1/2 3/10
3
2
+ 2 + 1 1/2 1/2
4
0 1/2 18/35 3/35 1/5
5/2 3/2 1/2
1/5
7/2
0 2/5
1/2 1/2 3/5
2
3
+ 1 + 2 1/2 1/2 + 2
+2 +2
1 3/2 4/35 27/70 2/5 1/10 1/2 1/2 1/2 1/2
3/2 + 1/2 1/5 1/2 3/10 2 2
+ 2 0 3/14 1/2 2/7
+ 1 3/2 4/35 27/70 2/5 1/10
1/2 3/2 1/2 1/2 3
4
0 3/7
3
2
1
+ 1 1 4/7
0 1/2 18/35 3/35 1/5 1/5
3/2 1/2 1/2 1/2 3
+1
+1
+1
+1
0 2 3/14 1/2 2/7
1 1/2 12/35 5/14
5/2 3/2
0 3/10 7/2
3/2 3/2 1
2 3/2 1/35 6/35 2/5 2/5 3/2 3/2 3/2
+ 2 1 1/14 3/10 3/7 1/5
+ 1 0 3/7 1/5 1/14 3/10
0 3/2 2/7 18/35 1/5
0 1 3/7 1/5 1/14 3/10
1
0
4
3
2
1 1/2 4/7 1/35 2/5 7/2
5/2
0
0
0
1 2 1/14 3/10 3/7 1/5
0
0
2 1/2 1/7 16/35 2/5 5/2 5/2
+ 2 2 1/70 1/10 2/7 2/5 1/5
1 3/2 4/7
3/7 7/2
+ 1 1 8/35 2/5 1/14 1/10 1/5
2 1/2 3/7 4/7 7/2
0 2/7
0 1/5
0 0 18/35
2 3/2
1
4
1 1 8/35 2/5 1/14 1/10 1/5
2
1
3
1 + cos

2 2 1/70 1/10 2/7 2/5 1/5

1
1
1
1
3/2
d 3/2,3/2 =
cos
3/7 1/5
+ 1 2 1/14 3/10
2
2
 1 + cos 2
1/5 1/14 3/10
0 1 3/7
1 + cos

2
3/2
d 2,2 =
3
1 0 3/7 1/5 1/14 3/10
2
4
d 3/2,1/2 = 3
sin
2
2
2
2 1 1/14 3/10
3/7 1/5
2 2 2

3/23/2

1 + cos
1 cos

0 2 3/14 1/2 2/7

d 22,1 =
sin
3
cos
0 3/7
4
1 1 4/7
3
2
2
2

2 0 3/14 1/2 2/7 3 3

2 = 1 + cos (2 cos 1)

6
1 cos
3/2
d
2
2
1,1
1 2 1/2 1/2 4
d 2,0 =
d 3/2,3/2 =
sin
sin
2
2
2
4
2 1 1/2 1/2 4
r
3
3 cos 1
1 cos

3/2
2 2 1
d 21,0 =
sin cos
d 1/2,1/2 =
d 22,1 =
cos
sin
2
2
2
2
 1 cos 2
3
3 cos + 1
1 cos
1

3/2
d 21,1 =
d 1/2,1/2 =
d 22,2 =
sin
(2 cos + 1)
d 20,0 =
cos2
2
2
2
2
2
2
Figure 32.1: The sign convention is that of Wigner (Group Theory, Academic Press, New York, 1959), also used by Condon and Shortley (The
Theory of Atomic Spectra, Cambridge Univ. Press, New York, 1953), Rose (Elementary Theory of Angular Momentum, Wiley, New York, 1957),
and Cohen (Tables of the Clebsch-Gordan Coefficients, North American Rockwell Science Center, Thousand Oaks, Calif., 1974). The coefficients
here have been calculated using computer programs written independently by Cohen and at LBNL.
3/2

d 3/2,1/2 =

Yl,m
Y0,0 =

2 !!!!

3
$%%%%%%%%%

Sin@D
2
2
3
Y1,0 = 1 $%%%%%%
Cos@D
2

3
Y1,1 = 1 $%%%%%%%%%
Sin@D
2
2

Y1,1 = 1

1 2 $%%%%%%%%%
15
Sin@D2
4
2
15
Y2,1 = 1 $%%%%%%%%%
Cos@D Sin@D
2
2
5
Y2,0 = 1 $%%%%%%
I1 + 3Cos@D2M
4

15
Y2,1 = 1 $%%%%%%%%%
Cos@D Sin@D
2
2
15
Y2,2 = 1 2 $%%%%%%%%%
Sin@D2
4
2

Y2,2 =

35%
3 $%%%%%%%

Sin@D3
8

105 %
Y3,2 = 1 2 $%%%%%%%%%
Cos@D Sin@D2
4
2
21%
Y3,1 = 1 $%%%%%%%
I1 + 5Cos@D2M Sin@D
8

7
Y3,0 = 1 $%%%%%%
I3Cos@D + 5Cos@D3M
4

21 %
Y3,1 = 1 $%%%%%%%
I1 + 5Cos@D2M Sin@D
8

105 %
Y3,2 = 1 2 $%%%%%%%%%
Cos@D Sin@D2
4
2
35 %
Y3,3 = 1 3 $%%%%%%%
Sin@D3
8

Y3,3 = 1

3 4 $%%%%%%%%%
35
Sin@D4
16
2
35%
Y4,3 = 3 3 $%%%%%%%
Cos@D Sin@D3
8

5
Y4,2 = 3 2 $%%%%%%%%%
I1 + 7Cos@D2M Sin@D2
8
2
5
Y4,1 = 3 $%%%%%%
Cos@D I3 + 7Cos@D2M Sin@D
8

3 H3 30Cos@D2 + 35Cos@D4L
Y4,0 =
16 !!!!

5
Y4,1 = 3 $%%%%%%
Cos@D I3 + 7Cos@D2M Sin@D
8

5
Y4,2 = 3 2 $%%%%%%%%%
I1 + 7Cos@D2M Sin@D2
8
2
35 %
Y4,3 = 3 3 $%%%%%%%
Cos@D Sin@D3
8

35
Y4,4 = 3 4 $%%%%%%%%%
Sin@D4
16
2

Y4,4 =

3 5 $%%%%%%%
77%
Sin@D5
32

385 %
Y5,4 = 3 4 $%%%%%%%%%
Cos@D Sin@D4
16
2
385%
Y5,3 = 1 3 $%%%%%%%%%
I1 + 9Cos@D2M Sin@D3
32

1155 %
Y5,2 = 1 2 $%%%%%%%%%%%
Cos@D I1 + 3Cos@D2M Sin@D2
8
2
165%
Y5,1 = 1 $%%%%%%%%%
I1 14Cos@D2 + 21Cos@D4M Sin@D
16
2
11%
Y5,0 = 1 $%%%%%%%
I15Cos@D 70Cos@D3 + 63Cos@D5M
16

Y5,5 =

Y5,1 =

1
16

165 %
$%%%%%%%%%
I1 14Cos@D2 + 21Cos@D4M Sin@D
2

1 2 $%%%%%%%%%%%
1155 %
Cos@D I1 + 3Cos@D2M Sin@D2
8
2
385 %
Y5,3 = 1 3 $%%%%%%%%%
I1 + 9Cos@D2M Sin@D3
32

385 %
Y5,4 = 3 4 $%%%%%%%%%
Cos@D Sin@D4
16
2
77 %
Y5,5 = 3 5 $%%%%%%%
Sin@D5
32

Y5,2 =

VECTOR IDENTITIES4
Notation: f, g, are scalars; A, B, etc., are vectors; T is a tensor; I is the unit
dyad.
(1) A B C = A B C = B C A = B C A = C A B = C A B
(2) A (B C) = (C B) A = (A C)B (A B)C
(3) A (B C) + B (C A) + C (A B) = 0
(4) (A B) (C D) = (A C)(B D) (A D)(B C)
(5) (A B) (C D) = (A B D)C (A B C)D
(6) (f g) = (gf ) = f g + gf
(7) (f A) = f A + A f
(8) (f A) = f A + f A
(9) (A B) = B A A B
(10) (A B) = A( B) B( A) + (B )A (A )B
(11) A ( B) = (B) A (A )B
(12) (A B) = A ( B) + B ( A) + (A )B + (B )A
(13) 2 f = f
(14) 2 A = ( A) A
(15) f = 0
(16) A = 0
If e1 , e2 , e3 are orthonormal unit vectors, a second-order tensor T can be
written in the dyadic form
(17) T =

i,j

Tij ei ej

In cartesian coordinates the divergence of a tensor is a vector with components

(18) (T )i =

(Tji /xj )

[This definition is required for consistency with Eq. (29)]. In general

(19) (AB) = ( A)B + (A )B
(20) (f T ) = f T +f T

Let r = ix + jy + kz be the radius vector of magnitude r, from the origin to

the point x, y, z. Then
(21) r = 3
(22) r = 0
(23) r = r/r
(24) (1/r) = r/r 3
(25) (r/r 3 ) = 4(r)
(26) r = I
If V is a volume enclosed by a surface S and dS = ndS, where n is the unit
normal outward from V,
(27)

(28)

(29)

(30)

(31)

(32)

dV f =

dSf

dV A =

dS A

dV T =

dS T

dV A =

dS A

S
2

dV (f g g f ) =

dS (f g gf )

dV (A B B A)

dS (B A A B)

If S is an open surface bounded by the contour C, of which the line element is

dl,
(33)

Z
S

dS f =

dlf

(34)

(35)

(36)

dS A =

dl A

(dS ) A =

dl A

dS (f g) =

f dg =

I
C

gdf