24

24.1

10.2.3

12.5.2 13.3.2

{y (x)} x

y (x) F [ y (x)] F [ y ]
F [ y ] {y (x)}
{ ( )} = ( x, y, z )

10.2.3 (10-4)
E [ ( )] = H d d (24-1)
( ) E
E[ ] { ( )}
{N l ( l ), l = 0, 1, 2, } l
l + N l
12.5.2 (12-23)
ln [N l ( l ), l = 0,1,2,...] = N ln N N + l N l (1 ln N l ) (24-2)
g l = 1 N
N l ( l )
l = 0, 1, 2, ln ln [N l ]
{N l ( l ), l = 0, 1, 2, }(24-2)(24-1)


 24-2 24

dS = 0 d 2 S < 0 F [ y ( x)]
{y ( x)} F

10.2.3
13.7.4(2)

24.2

1 A( x0 , y0 ) B ( x1 , y1 ) 24-1
y = y (x) y 0 = y ( x 0 ) ,
y1 = y ( x1 ) AB L y (x) L[ y ( x)]
x1 > x0
L[ y ( x)] = 1 + y '2 dx y ' = dy ( x) / dx
x1
(24-3)
x0

L[ y ]
y (x)
24-1
2 AB l (l > AB)
AB
24-2
A (0, 0) B (b, 0)
y = y (x) y (0) = y (b) = 0 AB
S y (x) S [ y ( x)]
b
S[ y ( x)] = y ( x)dx (24-4)
0

l
b
0
1 + y '2 dx = l (24-5) 24-2

(24-5) S [ y ( x)]
y (x)

y ( x) ( x)
y ( x) y y = ( x) y ( x) y y dy y ( x)
x y
 24.2 24-3

d y d[ ( x) y ( x)] d ( x) dy ( x) dy
= = = (24-6)
dx dx dx dx dx
d/dx
F [ y ( x)] F [ y ] F

F
F =
y ( x ) dx (24-7)
y ( x)
F / y ( x) F 1(24-7)
F F ( y1 , y 2 , , y i , )
F
dy i (24-8)dF = i
y i
y1 , y 2 , y (x)
y ( x)dx
dy i 2 F 3 F
F [ y ( x)] y (x) F
y (x)
F [ y ( x)] = 0 (24-9)
(24-9)
F y, y x
x1
F = x G ( y, y ' , x)dx (24-10)
0

G
x0 x1 (24-7)
y0 y1
x1 F F x1 F F d y
F = x y y + y ' y ' dx = x y y + y ' dx
dx
0
0

x1
F x F d F
= y + x y y dx
1

y' x y 0 dx y '
0

y(x) x0x1
(24-9)
x F d F
F = x y ( x )dx = 0 (24-11)
1

y ( x ) dx y ' ( x )
0

y(x) x0x1

1
[dF[ y + ] / d ] =0 = [F[ y] / y( x)] ( x) dx

 24-4 24

F d F
=0 (24-12)
y ( x ) dx y ' ( x )
G
G d G
=0 (24-13)
y ( x) dx y ' ( x)

1 (24-3)(24-12)(24-13)

d L d y '
= =0 (24-14)
dx y ' ( x) dx 1 + y '2

y ' = C1 y = C1x + C2
y y0
y = y0 + 1 ( x x0 ) (24-15)
x1 x0
A( x0 , y0 ) B( x1 , y1 )

2
(24-4)(24-5)
S [ y ( x)]

S [ y( x)] = S[ y( x)] + l[ y( x)] = 0 y + 1 + y '2 dx

b
(24-16)

1(24-12)(24-13)
y ' ' 1 + y '2 = 1/ ( )
(24-17)
3/ 2

y(x) y'

24.3

1.
10.2.3 (10-4) [
(24-1)] E H
E
(24-1)

9.4.2(2) H
0 , 1 , 2 , , i ,
E 0 E1 E 2 Ei
 24.3 24-5

= i ci i (24-18)
H
I 0
I = ( H E )d = H d E d
0 0
(24-19) 0

(24-18) i H i = Ei i i j d = ij
2
I 0 = i c i* i* ( H E 0 ) j c j j d
= i j c i* c j ( E j E 0 ) i* j d
= i j c i* c j ( E j E 0 ) ij = ic i* c i ( E i E 0 ) (24-20)
c i* c i 0 Ei E 0 0 I 0 0 (24-19)
(24-1)
E = H d d E 0

(24-21)
E 0 = min E [ ( )] (24-22)

E
0 E 0 E 0 (24-21)

(24-21)
E [ 0 ( )] = 0 (24-23)
E 0 0 ( )

2
I 1
I = ( H E )d = H d E d
1 1
(24-24) 1
(24-20)
I 1 = i ci ci ( E i E1 ) = c 0 c0 ( E 0 E1 ) + c 2 c 2 ( E 2 E1 ) + (24-25)
(24-18) j

d = c d = c i ij = c j

j i j i
(24-26)
i i

E 0 0 (24-23)

ij Kronecker delta i = j ij = 1 i j ij = 0
2
 24-6 24

0 c0 = 0d = 0 E 2 , E 3 , E 4 , E1
(24-25) I 1 0 (24-24)(24-1)
E = H d d E1 (24-27)
E [ 1 ( )] = 0

E[ i ( )] = 0 i = 0, 1, 2, (24-28)
E [ i ( )]
0 1 2
E 0 E1 E 2 E 0
E1 E 2
3
(24-23)(24-28) 24.2

10.2.3
c1 c 2 (24-1) E
c1 c 2 (24-23) c1 c 2
E
E ci = 0 i = 1, 2, (24-29)

10.2.3
c
Rayleigh-Ritz
= i ci i n i n
E 0 E1 E 2 Mac Donald
10.2.4
4
{ ( )}
E [ ( )] E = 0 E
(9-57) = ( ) ( )
( ) -
 24.4 24-7

9.12

( )
{ ( )} E{ ( )} E = 0 E
N
( 1 , 2 , , N ) 3N ( )

(Kohn W) 1998 Nobel

25

24.4

1
12.4.4

24.1
ln [ N l ] {N l ( l )}

ln [N l ( l )] = 0 (24-30)
(12-24)
max
l( l ) N l

2
12.5.2(2)
(24-30) N l

l N l = 0 l l N l = 0 (24-31)
24.2 2
12.5.2 N l ( l )
(12-37)
N l ( l ) = Ne l / kT h
e h / kT (24-32)

 24-8 24

24.5

1
H i = E i i H
H ( 0 )
H = H ( 0 ) + H (1) + 2 H ( 2) + (24-33)
H (1) , H ( 2) ,
H i = E i i
(0) (0) ( 0) (0)

{ } =
(0) ( 0)
0

, 1( 0 ) , 2( 0 ) , i( 0 ) (j0) d = ij (24-34)

{E } = E
(0) ( 0)
0 , E1( 0 ) , E 2( 0 ) , (24-35)

i = i( 0 ) + i(1) + E i = E i( 0 ) + E i(1) + (24-36)
(24-33)(24-36) H = E i i i

( ) ( )
H ( 0 ) i( 0 ) E i( 0 ) i( 0) + H ( 0 ) i(1) + H (1) i( 0) E i( 0) i(1) E i(1) i( 0) + = 0
(24-37)

( )
H ( 0 ) E i( 0) i(1) + H (1) E i(1) i( 0 ) = 0 (24-38)( )
(1)
i
( 0 ) { }

i(1) = j aij (j0 ) (24-39)

(24-38) H ( 0 ) i( 0 ) = E i( 0) i( 0 )
j
( ) (
a ij E (j 0 ) E i( 0) (j0) = E i(1) H (1) i( 0) ) (24-40)
 24.5 24-9

i( 0)

j a ij (E (j0) E i(0) ) i(0) (j0) d = E i(1) i(0) i(0) d i(0)

H (1) i( 0) d

i( 0 ) (j0) d = ij

E i(1) = i( 0) H (1) i( 0) d (24-41)
(1)
E i

H (1)
(24-41) k( 0)

a ik = k( 0) H (1) i( 0) d (E ( 0)
k E i( 0 ) ) k i (24-42)
(24-39)
1
2
E p
E p(0)
E p = E p(0) + E p(1) + 2 E p(2) + (24-43)
E , E
(1)
p
(2)
p
,
A A ( 0 )
A 1 2 A (24-44)
A = A ( 0) + + 2 2 +
=0 2 ! =0
= 0 A = kT ln Z Z
(13-44)(13-46)
( )
Z = Q N ! 3 N Q = exp( E p kT )dx1 dz N (24-45)
V

Q N
(24-43)(24-45)
A ln Z 1 Q
= kT = kT
= 0 = 0 Q = 0
[
= Q 1 E p(1) exp( E p kT )dx1 dz N ] =0

E (24-46)
( 0 ) 1
=Q (1)
p exp( E (0)
p kT )dx1 dz N = E p(1)
(0)

(A ) =0 E p(1)

 24-10 24

24.6

1. . . : , 1980
2. , . , . : ,
1999
3. Levine N. Quantum Chemistry. 4thed. London: Prentice-Hall, 1991
4. Parr R C, Yang W T. Density-Functional Theory of Atoms and Molecules. New
York: Oxford University Press, 1989
5. , , , . . :
, 1990