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21

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k=!

2.1. ls ( )
ls ( )

25

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, ,

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~, (ML - LM)\jfn

26

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...~

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:

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=l

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f, j

27

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).

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f ,

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== /(, , z, , ,
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z,

t)

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(3.3)

. . -

30

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:

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31

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,
t F

:EUi(Xi, Yi, Zi, [).

"":'- ,"..-.-.. --.-.

F =-+-(HF-FH).
dt 11

(3.5)

F .

(3.4).

. ,

lI:, :

F
F

, . .
.

3.2. II

aHo

(3.1) :

1.

: )

2.

z;

"~n2

F:

l.

) ?

= J'f'* FPd't. :
F 011 '
H FKaK , I:!.

Pz

d2,

:.

=- 2 2 + V(x).

l1 '[1 ?
3. , , .

=.

})I F:

"

<Pi - ,
~.

F = F= dd 1'* FPd't = f '* E'f'd't + f '* 'f'd'C + f '* F ' d'C.

dt

d'f'* -' ~,t

dt
(2.1).

. .

4. , -

,
~n

5.

n.

, . (, , ); (, ,

6.

OI ,

F = J '* ~~ 'f'd'C + ~ J(1j* 1* )FPd't +I '* F(H'f')d't = .

i~~ ~~] 'f'd'C

=.f 'f' *(
-+-HF--FH
! . 1'1
1'1

32

2,5).

..

i1i

~~) = t), '

<()

(4.1)

= <().

4.1.'V

f(t) =

~~ ~ Me~

,
d

, J,~l?~ , ,'

, . q-;

(. -'

const e-it//i.

. ,

(2.1:

i1i

'(,

t) =

'(,

n <n(),

t),

'n(, t)

at
'(, t) -

; -

= <pn(x)f(t)

'Pn(x,t)

, '; t -

= <pn(.~)e~iE,;t/~:

,.\3 F,

BpeMeHJ4:. 0

, .. '(, t= ). u '

' n(,

, l : -;
,

q .

: r I.

F = J'P~(X~

-;

, 'l' , :

t)F'Pn(x, t)dx =

J<~()int/IiF<n()-int//idX =

= J<p~{x)F<pn(.i)dx.

'

, . :
(2.1) ,

t)

, t ( ),

I II,:iO , ~ '(, t) =

= <p(x)f(t). (2.1), "

i1i() af(!)'= H<p(x)!(t).

"

at

<()f(t). ,

' .

' -

!,'n ' n (, t):

n

:
:

in_1_ af(t)
f(t) at

34

= <() = .
< ()

35

!n'n(,

t)

. ,
-

= LCnIf'Pn(x~ () = LcnII<pn(x)e-int/h =
n'
'n
= L...~ {n (X)e-int/h
n n"t"n
,

(,. il , ).
- , '"
.,

. ,
:
. , ,

. ,

"4.,Z.

, u
1

, ;, o~

,
.

. , ~
():

M2i~' ( -

H' .

= f ''* (. ~ )2 'Pd't.

,
; ,

- ,
,

4.

: ..;

'1

f (*'* -

-,~

>

i.*'*)(.' + i.'f!)d't = f'P* / + /2

'Pd't;::

(4.21

~I (4.2)

,~ ' . ,

= -).

(4.4)

~ ,

"

= i(xp x ~) = -1'1 ; 2 ;

;:: 1'12/4.

t ,

.
, .
:

2
f'P* A2rd't + i.j'f1*(. - EA)'Pd't + ,2J'* E 'Pd't.

~, .'

,;

, I () -.
~

., l'

(4.3)

- 0,529 10-8 .

ljepaBeHCTBa,

-:

;:: 1'1/2.

+ l + . 2 .2 ~ .

. -I
,

'

1'1
>--=

V_

.:..'

2 '
,.

13 m .
, :

36

.
1,054.10-27
11 108
/
""
.

2.9108.10-28.0529.10-8
'
.',
'

1/300 .

<

().

37

 () t.[

II ' I
, , .
, ' .,

, . (

" ).
: -

- " .

t .

':

(4.5)

:~.',

Pt= ln dt (,

.
. , ,
,
, . . ,

. ':,,
, ,
, . :

" ~ :

J-

d (i1i d')t = i1i.

t(i1i
".
t ,,'
dt
CJ

t ; =in

:t

.
'

(4,3),

f'P*t 'Pd't + i'*(ft - ptt- in)'Pd't + /..,2f (! ') * (! 'P)d't ::::

2

f 'P*t 'Pd't + '*i(tt - ptt)'Pd't + Mf~~'Pd't -: /..,2 f <! ');*(! 'P)d't.

2

! ,

-1. lf~ ~ Ce i (p1)/h (

) .. , q, 9
.
., "
2. I~ : /6 '?,
. ' . " ' , ' .. ,
"'
,
3. i.~ C\<I'\ + ~2<1'2 2<1'\ - ~\q,2, ~ \
2 i, lf <1'1 <2 -

4. . jj =-0,3 /2 =-0,77.
),
\jI = \<I'1 ,il/,h
(<1'\ lf <1'2

jj

+ C2<1'2 eo,77it/h

/z)

5: ; ~:k<l'k()-iEkt/h
i

= (! ')

- .
, pt'P = '.
-to, Jj - , -
: . '1'.
, = '! - ptt)

38

n,

6.

F i~.,
\jI(x) = L,Ck<l'k(x)e-ikf/h, 1 , -

.... '

i "

'I'(a) = sin(ka) = . , ka = mt, n .

,

n ,,;

'.

sin(-mtx/a) = -sin(mtx/a),

n;

. ,

= 1, 2, 3,

...

'

I;i :

:
,
'. : ,

:
,
, , "'"
.

yro .

(. 5; 1). ,
< < ( ) ()
,
( 1, I) () = 00.

tf [, ],

:'f()

=0" 'I'(a) =

, , II ,

ri'd .
II ~'' i -

c2 1i 2

= - 22 n2 , n = 1,

(5.1)

2, 3, ...

,
, (5.1). n

.

21 sin 2 ( nr)clx =J.

",

1air 2/;

, 2 = /2, '
,

,'

"', "

'

.:

5.2

~ ,

k 2 = ,2

2
1i

2 ( )'

'1'() =_k,'1'
.
2
2

11

1i -

111

5.1.

40

'1'(0)
,

= .

, 9

'l'n(X) ";0

~~ , . ~
, ~.

,!

'

, lI
n -n - 1 =

E 1(2n - 1).

.,

, ~

'I'(x) = sin(kx + ).

Ii: ,

n- , : q ,

~ B~y

. ~

jf. '
, ..

. .

41

"

1
.

5.3.

II

..

~.

III

fJ<:\ iI

~ ( III). ,
I 2, = .
,
; 5.2. , I1 n = 1
(l),2.C2), ~(); -!lJ;.I .

Ix ~. , ~ ~

;'
I. ,

.;'.(

;, ,
.
,
, (
) (n - 1) .
,
r.f .:.

,
.
(, ,
J:l ). .'
,'"
. .
u II '
:

<),:~ u u
.

.
, ,

'(/ = 1/2).
'V2(X) , = /4 ) = 3/4,
= /2 .
, '
, , ,
' ,
( ); ,
, . ' u (
). 1I , -

J.r = /2.

, , ,,2 = 2

2

'

2'V() __k 2 . ('.' )

2 "''v .
'V() = Acos(kx),
'V() = Bsin(kx).

III:

'

, ,
: u (. .
).
.
, ,

"

, ri

=
= ~ ":' ( 1),

(. 5.3):()
-

42

<<

( ) ()

43

t.J: ,
.

. -.rp

' . +

.
1 III.
,
.

1 III .
,

'J1r{)
-. 1 ,
,
, +
re CCOOTBeTCTBY~T! ~;e'p;iI,' 11; !i:~ - - .

'vix) =

(j; :,, I~I ..,

, ~. II~ .. , !i,Iirl'

q =. ffl ",(.) '''v~() .

~ s:rI.I? -

~.1': :
",iI ()

",()

'

. ",i()
=

/()

"'() "'() ,
:

'(2 = v 2

ktg(ka)

; .

7'.-'{',

= .Jv

k2, -

5.5.

- . fJ

k 2 ,
2-

.Jv 2 -

k 2 ktg(ka) ":'ktg(k)
"f: k = 2,53, 5,02, 7~33. :,
i 1 == 3,20 .., 2 = 12,60 .., = 26,86 ..

kctg(ka)

1 .. 36 .. (
I:' . 8). . 5.4
~
, ,
".
'

= '(

ktg(ka)

~
, n. ?
-
.

Ixl ;?: aj2)

kctg(ka) =

.Jv

2_

k2

(5.2)

(5.2) -.rp

. ~
jJ

v ,

14

12

'( = ktg(ka), '( = -kctg(ka).

10

6
4

2
n -

1).
, Ie Ii
! < 2 < ...
,
.
, -

44

5.4.

: (v 2 -

-kctg(ka) (3)

k2)!/2 (1), ktg(ka) (2).,

k.

45

/
i

'1'"

1,2

..

"

10-

1,2, ... ),

Pt;tm Hn(~). "

0,8

1 = 2n (n =

(5.3)

0,4

" - i .

q n:

-0,4

-0,8 '
.

.~"!

., 5.5. ~ \jin :(;"*~fI

='

\jfl (~) = 1[-1/4.J2e-~2/2~,

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

\jf2(S)

:i: == l' . : (
,
, ;iIe 1)

= mro 2 2/2. ~

= 1[-1/4 _1 e-~2/2(2 -1)"

,;

.J2

'

\jf (~) == 1[-1/4 _,

1 e-~2/2(2~3 - 3~).

IIJ. r:
~)) 7 ,

(:)

\jfo(~) == 1[-1/4e-:~2/2,

"

-1,2 L-~~":'-"';";"';'J..;.....O,----"J--':;""":"'-";"""--"...J..---'---~
""11~5 ,J,O ' ::;-0,5'
Q
0,5
1,0
1,5'

..r

1<; ,
. ~ : ,

I:Q ::, .,
\

,"

' ",

, 10- 1 = 2n

ro

= --,
2

'

\;

" =ro( n+~)= hV( n+~)-

(5.3)
, ~ -

~ ,~ ~2
. ~ ~ ~ 00

= e-~2/2.

"

\jf(~)

' ,'"

' (5.3)
,

"

\jf(~) = e-~2/2 P(~). P(~)

ro 21[, v

> . mm ,
= ro/2.

, , .

. -

(. 5.~):

V(x) = (-2
= R - Re (R e -

- 2-

),

);

.
, , :
, ( - 1).

46

, :;t?
. . -

47

v,

..

\jIi

1
-2

1,0

-.

a(2Ajm)1/2

.
, ,

"'4

, , ,

n.

. 5.7 t5t

2 , .'

-2

, ,aJi,:l;r

-1,0

(-0,054 ) n = 17. , -f';

-4
-0,1

-0,5

0,5
1,0
R-Re , ..

1,5

, 0 n.
. 5.8

2,0

, ~~

. 5.6. (1)
: n (2), 1 (3), 2 (4).
; ;:: -4,747; -4,475 ; 1 -3,954 ;
~ = .,...3,466 ; == 2 104,7 - 1 ; 1 - = 4195,0 CMc1 ; ~ - 1 = 3935,9 - 1

>~ . n 2
. ,
6 . .

-0,0005

( 3,2 ),
-101 ' .
:

. (
V(O) = -), ~ 00 , :..

' '

.
:

t). 'f

n '=-A[l- ~~~A(n+~)J,
\jIn(~)

" ,

(: . J! .
, '
\ (,
-J1 .-

(5.4)

= e-~/2~s((~).

): = 2,J2mA
-
,'

"

<,): < 00'

-~

(
.

5.6

-3

-5

1 z ( + 1) Z2
, "(, Z = + - -1' + ,,(
1) 2' + ...
,
1 l~+
.
)

n=

-4

( ) 5'

, 1, 2.

48

-2

. M~cca '; (O(~) == F(-n;'2s+ 1, ~)

--------------------------------------------

-1

s= ..r:::.
n = ,J2mA, - (s + .!.). ,
'
'
2 '
-

-0,5
,-'.

5.7.

0,5
R-Re ,

1,0

1,5

2,0

..

I 2
(

(5.4

49

. ,

2,0

'Pw/X' t) = ] C(k)'Pk(x, t)dk = ] dkC(k)eikxeink2t/2m.

(5.6)

C(k)
=

k1i

, ,

10
.

5.8.

20

30
40
. R":"Re, ..

50

60

, .
, C(k) k = k o

70

Bl:fe

(, )

C(k)

n= (1),

= ~ 2;/2 [-

(\- ko)2

1 (2);,2. (3)

(5.6)
).

Ml;{OrOaTOMHbIx , ,{

'I'I .
l ~ : OJ .
'IIt~
, 'I I:I
0 '{I:I - Q .
'I
(V(x) = ),
:

'l'wp(x, t)

-1/2

=,n [(1+ 2 J]
1

::

i1it

1/ 4

)2k

-hkot /
i1it
(
iht) + 1 - 2 2
2 2 1 +--2

(5.7)

(5.5)

'1' k(, t) =

e-it/h/kx
.
,

h2k 2

=-

2 '

k -
k = /h.

, ,
, Qrp -

50

= hkot/ (5:8)
. ,

v = x/t

= hko/.

. , (5.8)
,2 2

.,

)~1/2

= [ (ln2) ( 1+ ~2~4 IJ'

51

'P wp

ct , -

0,6

0,5
0,4

0,3

1.
0,1 1
: ) = 0,5 , n = 1; ) = 0,25 , n = 4.
2. + 1 - n fI

0,2
-~

0,1

?
3.

-3
.

-.

5.9.

-1

.
, I;I.

. ,

m 2 / n.
, vt = koa2

(5.7)
(5.5). , ,

1,5 .. 5 ...
4. = 10 , . = 2.
5.
= 2 .., . = 0,01 = 2000 ..
6. =4,76 , . = 1,05.
7.
= 4,76 , . = 1,05 = 1000...
8. .~ () .lIO
~ ~I. KaKO~O l 5,!/3() ~
l:j' ?

9. . ,

? .

.\

. ,

n2k?; .

, (
), , ,
,

.

vt, ,

; ,

.. , Q;
., .l ..,

* ,

.
.
, Q

52

, -

(l . .
2

._

t;2 = l1Q = 27,211

1 .. .

~ = O,0529177~M ) . 1840

, . .

1 840

. .

"

'(). {ai} ct
'().
L-, BJ1Y, () -

BJ1e

L,

{b i }

()' L-. ~<x), () -

~! '() , -

, . ":

I1 ~
L, <Pi(X).: . ,.

, :i ~ : KOOP~Ha! :
, :Ie KoopQ?l:HaJrJ1:IOM :"
, . -.'

, : ,. ; ~

'() =2A<PJx).

=[:~. ]; =[~],

(61)1

, ~

.I .' ?,. . . -.

. , .
v

L, i q./I

<Pi:

F=

= 2:bi<Pi(X) = 2: ; <;().

~ ; , ,'

Fl

F2

Fi

F23
F

""]
'"

='LFkiai

(k

=1, 2, ...)

= 1, 2, , .. ).

Fi2
.F21 F22

<) (k = 1, 2, ... ) . :
. b :

(6.2)
bk

: -.

; = 2: ; J<Pk(X)F<Pi(X)dx == 2: Fkiai (k

F '(): () = F '(). !

. ..

:, : F;k == <p;(X)F<Pk(X)dx 'j.

t (), R -j

()

; = J<7()'()dx.

:.

'..

(6.2)

B:;;.FA
, ( () L-)

( '()! -

'()
.

=2:ai<Pi(X). , -:
i

"

(j>i(X) 1 . ,
ai, ~ '()
{}, . . {ai} -,
54

),

F),

L-. ,

() =

F'()
55

, i

F :";

'I'().

F22

Fi
F2

F2

Fi2

;j

=F

... ]

...

".

.' .:.,~.

F* , (F*)ij =; n'L,:
~

F;

, ~i

I F : . = F ... ,
!l F+,~+~~ ~ (F+)ij= (Fj;)* ~ M~;~J
, F. (F+)ij = Fij , F
n:>f:~ ,um. , ~

(.4).

LB

L-:
'

(5.1).

'

, .

KpOHeKep~
0ik = 0k: Oik = 1 i = k; Oik;: ri i::f::. k.
j! .

Lik

L = l:l:a7Lijaj
i

=2, lil aiI

2
.

j,

I;I ~
'

'():

f:r*(~)'P(X)dx = 1.
l3 tp, l:iriiIy (.1), '
'lO <r>i(X), "

L ik

=J<r>7(X)bpk(X)dx =J<r>mk<r>k(X)]dx =
(.3)

= IkI <r>7<r>k(X)dx = lkoik'

J'I'.,. *()'I'()~=2, 2, a7ajJ <7 (x)~j(x)dx= 4,lp;( == 1.

'i

j'

, , L
.

( )
F. ,

F =J'I'*(X)F'l'(x)dx,

F -

(.4)

( )

F , '1'.
, I1 L-
(.4) ~:

F = l:l:a7aj J<7 (x)F<r>j () = l: l:a7 Fijaj

i

+ = (ata2a; ...)

57

 . . ;

2
Llail =1.

. , L.,GI, . .

; QGr

: , B~

~e ,

<1'/1

Z.

'1';, ,
:

F = Llail2Ji,

'1'; =

I' Ji

~:';I .

~ ~

, ' U,
'l'i m l>r:

Ji, TOjj
ai co~

, .

L. </1U/1;'
/1

f 'l'i'l' jdx ;= L L (U/1; )*Uvj f <I'~<Pvdx =

/1 ' v

I":Ji ';I':

= LL(U+);/10/1vl:rVj

. TpaKTOBl1,j

(:m; . , s;
<

/1

= L(U+);/1UW = .

(6.5)

/1

U+ - , U: (+);/1 = ;;.
,l;j. :

Q . ,

, ;;

'I'=<pu,

.:

, ~ Ji;
,

I ~ ,

9 "'
.
.
",.
;,
Jjl i.

', J

(6.6)

",+'1' = U+<p+q,U = U+.-:=: u+u;, ;

1 - , ~j == oij. .,'
(6.5), (6.6) , U+ - ,
U: U+ = U-l< , (
I -
),
, );,. .(;
Q~.

: 11 1 ),
. ~

F;J'J!) = f'l'tF'I'jdx= LL(U)~;VjJ<I'~F<vdx=

, ,

, : (

1.

/1

= LL(U+);/1~)UVj

~ ( i
bracket, , ). ( 1 ) .

/1

. .

'

= (U+F(<I/)U)ij

(6.7)

('1'; 1 '1') == '1'7'1'jd't.

:/

n
. , -

,'
58

F('J!)

59

, I

: Fjo/) = /;: , ~
F:
. (6.7) ,
,
;

Ii

x+r02x=O

SpF = LF;i'
;=1

l, ,
,

;=1

;=1

SpF(o/) = LJ
" P~o/)
= LJ
" LJ
" LJ
"(+).1/.1. F.(<P)U
11
~y
VI

()mn

~=1 =1

(6.8):

= -i "2JHmk Xkn -

=L

L ~~<P)O~y

~=l =l

=L

11.

FJ:)

= SpF(<P).

3fI()~n = ')mn()mn = -ro;'nmn' ,

.
,
:

.-. . d 2 0)2
=--....-+--
2

dx

= -11.i (Erxmn - mn n) =

~=l

XmkHkn)

=!....(m .,... n)mn = ')mnmn'

~=l =1

.,.....

). -

11. k

,;=1

(3.5)

'.,.....
=- ( ~

=LL~~<P)LUv;(U+);~ = LL~<J)I~v =
~=1 =1

(6.9)

-- .

+ )2mn

") mn
(

(6.8)

n
nn

(6.9)

. 2
()

2
-:- )mn
)x~? --

,, mn .

, )mn = )

, n

0)11..

WN
. ,

(6.8) , :
; = i: = mi (

, KOTOP:~ . .lf~

),

n n'

Ix
.

= jJ ==

-vv

2ron, 30)1i,4ron, ... ,

.,

(r02 - );'n) = ,'

' . -

, ,
mn : mn

= nm '

mv = =-VV.

n1'
n
,
:

2
)
2
V ----

60

F =

. = -1-.
.n

61

, ( ,
, nm

- mn :

1.

.... , 1
+-n
0,64.
2

"

.
2.

<!,

:4,

<2, <t',

, r

(n +l , n)2 = (n , n_l)2 +-2 .

3.

:4, . 2,

, n,
. ,
, lI

-1
, ' (l 0)2 = iz/(2).
, ,

(n

"

n_l)2

n'

= -2'
,
'

.
2
4. 1'~ -K~
+3, +5. \ ,

n , n-l

~1i
= Xn~1
. , n = -2'"
.

~
:
~

= '2 )2 +
2

(6.10)

r. <;
r (6.10)
,
'

;). -

62

5.

,1;

5)

~ , ; ) os' ~i).

6.

, .

0,59

5 =: cos2e (

: )

).

'40]
0,70 .

;
81t

s <

i'i'

V
4n s s <t' -

~2

~2

~2

/ :::

~2

~2

+ l + /z.

7.1.

[1

~12 ::: -n2'\162 ::: -n 2 -,- (,s-.

.
) +--,-'.
J'
'1'
sin

sin 2 aq>2

(7.3)

1-!I

~ :

, -

1 ==.

, ( -)::: i/i. , ; [,

Zy:

/ == : - ZPy, / ::: ZPx - xP z' /: ::: - '

:

;.. . .

~'::: -ln. (
)
Y--ZdZ

.
(jz'
~/: == -ln. (
).
-

2 .....

",2,,-

.....

_.....

_.....

== /'{.: -ZZ) - YPx(ZPz - pzZ) :::in(x.p y - YP.J == iN z

'

~/::: -ln (
)
Z--x-

==YPx(PzZ)-Z PxPy-z+/Z z )-

(7.1)'

, lx,ly .
,

.
:

[/x,ly]==in1z,

- .

[/z, lxl == ihZ y ,

[/, lz] == iliZx.

(7.4)

.
(7.4):
~

~2

~2

~2

::: (ihl z + lylx)ly

64

~2

~2

~2

~'

/x(lx + / + /z)- (lx + l + /z)lx ::: lx/yly + /xlz/z

(7.2)

-///

~.

-lzlzlx

'

-ly(lxly - i1il z ) + (/zlx - i1il y)lz -/z(ihl y + /x/z) =

= 11i(IZly + //: -Iz{y ,. -Iyl z ) = .
65

. , . /.)

lz

1.

. (7.6) ,
i , L= Z(l+ 1); / - I
I 1 2: Iml. fi

[l,Zx]=O"
2

[l , Zy] =

~Iml cos 8 -

[l,lz]=O.
(

<: QR , 11
, .

, z

(2/ + 1) (l-Iml) !p,lml cos 8,

2 (l +Il)! '

(8) =

(7.7)

::

1
d l +1ml
,
2
p,lml cos8 = -sin1ml 8
, I I (cos 8-1).
,
2'/!
(dcos8)+m

'

: : . ,
, Z,

l,

: (7.7) 1
( ):

7.2.

",

m , 1 lz , I'

~. ..

(.

1z

2):

1e1m'l'.
.
__
.. ~

",(8,<)

L;

. ~
, ,

<)=

l,
~ ;
{
=' (-1), <.
.
(7.8) (_1)m ~

, e~.
2

= 0(8)(<).

yi

z 2'"(

< )

.("s 8 ",(8,
-_ -*-2 [ -1- sin 8
8

<) +. -12- ",(8, <)] =

sin 8 <2

yi

== L1i 2",(8, <),

2 i

L1i2 1'
( 1i 2 ), j

0(8):

_.1_~(sin8d0(8)+[L_~0(8)=
.
s 8 d8
'. d8
.
s 2 8
66

.';I / = , 1,2.
1
.n'

cos8,
, = V~

8' ilP
-3.
s
,

~81t

(7.9)

2 = {5 !(3cos2 8-1),

2 ! =

(7.6)].

V~2
241t
~

+.

- . 3sin8cos8e-I'I',

:2, 2 =

5 3. sin 2 8e2i'l'.

961t

67

~2

s, , d ., ']
i

>'l;{

:
,

dz;

z
-(3z2 - r2 )

' dx2 _ y2

.J3 ( 2 ;,.. 2)

l'

(7.9)

dxy

.J3xy

dxz

.J3xz

.J3YZ

dyZ

:.,1:

.,'

r'

>'

s(s +1)/i "

= 1/2,

1 ' . ".
= ..:../i
. .
2 '

'

Sz

m.() ,

:
l/2 (1/2) =

(7.9). t~
, ' aj

"

1, .

112 (-lj2) = ,

-:-l/2(-1/2) =

-l/2 (1/2) = ,

.j

..~

-'1

($ -

, +1/2, -1/2. fI-

, d
.

1.

I;I<' XJj2 (1/2) -l/2 (-1/2)

. ~ ;

, :i :
. , .

( ~:
..

f (X~dcr
,

cr=I/2

-7

l/2()-l/2(') ==

cr=-1/2

=,r sin cos ,q>,

= l/2(-1/2)-l/2 (-1/2) + l/2 (l/2)x-l/2 (I/2) = ,

= t sin esin <,

z =r cos ,

'

"

. Sz, .

., +1/2 -1/2,
=

cos(m<p) i sin(m<p).

( ~ .

,
(
, ' : 1),
.

.'

~~

, , ,

eimq>

'.'

"

Sz -'- ms/i

,,...

, I :~{ .

.....

S ,Sx,Sy, Sz. I>I

7.1.

7.4.

IyI: . . ,
He~OTOpoo .

7.3.

, ~
, l\1

. o~

s. , "

v
m

2

lz.

, ,

" pal~oo ; -

69

. !?, ~

"' [}+' }z] = -0+:

,(

(, ). .;;

09 KO:d

[}+,lz1\jfm = j+jz\jfm - jzj+\jfm = -f+\jfm.

, ,
. ~ ,j

qr ,

m ,

KOTOPI;>Ie

( , :

}z

"'

"k{ .
-i

}zO+\jfm) = ( + l)(}+\jfm), '

z..

, :iP~ l1ui~:, i . :.

, ,

, $l ,

} + "',

j.

(.
,

"'+

j ).

yti :

[}, f y ] = ilifz;

[} fx]

= i1ily; [},

fz]

= ilifx

1,

, .>q

";2

[j, jy]=O;

. (7.12)
,

\Vm

j+

yio

, ()

. , .

: :

[j, jx]=O;

, -

(7.10~

m J

I , g

.. 2
:,J

} z ,
( + 1), .

[j, Jz]=O.

(7.11~

IM , , nuu

f_, ~a "', \jfm-l:

'"

,..

.'

,..

j+=j+

} - l; = bm\jfm-l:

,..

i_=jx-ijy .,

= [}, }zl+ i r]y, }zJ= -ili}y + li}) = -Ii + i}y) =-li}+,

[}_, }z] = [}, }z]-ir]y, }z]"; -ih}y -li}) = Ii -~y) =Ii}_.,
[}+,}J = +i}y)Ox ~i}y)-Ox -i}y)(}x +i}y) =
, .~ 2i(jy}x:'" }xly ) = 2tz}z.

,..

0+, fz]

j+

j_

j .

j+j_

,..

'2

.... 2

"

"

jxjy) =

= j + j + j <'

j == j+j- - jz + jz

'.

,
2

j =j-j++jz+jz

= ",

( ,

70

..... 2

"' , l': r4

"'.
j z\jf 111

= +) -ijy) = jx + jy +i(jyjx = j + j - i(ij <)

~ i~ } <. : ~

,}

j+j_

(7.13)

Ii

= 1).

71

 . (

, :

f \jI~,]+\jId't =f \jI~' ~1 + iJy)\jId't = \jI~ 1 \jId't)* + i (J \jI~ 1\jI,d't ) * :

= (J \jI~ 1 \jId~ - i f \jI~ 1 \jI ,d't ) * ~ (f \jI~ 1_
\jI ,d't ) * .
' =

\.

+ 1,

J\jI~+! ?+W!1Jd~ =

! , ~ft
(::: j) (

,"

7.5.

=(J \jI~) _~+ld't) =:I+!'

If ' "' q
.

], , .
'
2

Zxa.Kj, , j

\jIj' -

\jIj =

l>{ .-. -

'

1I
:'
.
,.,

"

v,

J( J + i),

.
:

, ,

J
J!, jlJ . ... , jN, ln!, 2; ~ .. , N,;' 2 '
J,

(j ), = j(j + 1) = (j-jJ, + (jz), + (jz), =

=

'

, .

/Z ~ }z! +)z2+"'+ }ZN'

j :

,',

z:

, 2

j(] +1)n \jIj.

I qIa,

,
,

.!,

' ji (i = 1, 2, ... , )'

j!(j! + 1), j2(j2 + 1), ... , jN(jN + l)., t,

1=1!+12+ +1N

;t
2

'

. ;.,.
2
.
.
.
..,'

.,

=(1-1++1z+1~)\jIj = (j+P)\jIj =j(jf.l)\jIj'

,,;
;'-"

:
. , N:

~, '

12\j1j

= :"'}) :0

'

d; 't~ 13

= ~ + )(j -+ O~'

, I

. '-,'

Z : .

' , :. '.

~,.,

I<:

I(}-),'(}+)', ++ 2 =+! ++ 2
'

~2

J i .

.
,

+ ! = ,

a~ = j(j + 1) - ':':' 2 = (j + )(j - + 1)

= !

+ 2 + ... + N'

.
,
TOJfbKO , aiI ,

.. .

72

'

,
73

 f"q f
:

1,

, ,

j2'

j\, j2

...... 2

, 'l3qjt!.~
Q. (Jl',~~;),~Iti811111111
1 , ,
'.

',

, , ~

. , , ,

21 + 1. ~ ; '. ]~

J(max)

{2j! + 1)(2j2 +J)I , .

~qG~,

L.

!, 2' (2j! + 1)(2 + 1) ~

~ ~~ ~2 HOB~,
, 'I

1,

"

7.2).

" +

. 7.2,
. MQ~HO , "

(21 + 1)

(21 + 1)

1,

li,~r

_ J(min)(J (min)- 1)+ \ + j2 - J (min)+ 1). "

, !~~1'\1,1(:

(2jl + 1)(2j2 +1), IiQ1B6~#tt

: J(min) = \jl - \ ~I,j9If~
I

, i/'t~tt~ ,'"
, . , ~!9". '
: , xao]J~Wr .
)), j2, J J.&

' ' 6' 'Ix ml, '

(2J + 1)= l + j2)Ul + j2 + 1)-

J(min)

: ,;N-

.,""""'!

ll' ei (.

lVJ'LnllO'"

, "
Z. '

(7.141) .

, == j\ + j',
'

, :

; !. ~ 1

"~2:,
7 .6~ J . "

'

".

J. ~.
J == jl + j2 - 1 ,
, )J( 1 =j! + j2, 1
J = j! + j2 - 1.
1
, l:l, q, , 1

, 1t
,

\,j

j/ (i = 1, 2).

7:,~

>j11nJ >j2m2 ():::: -jl' - + 1, ... ,j); ~2 =

:::: -j2' -j2 + 1, ... , j2)' (2Jl +
+ 1)(2j2 + 1) - >m1>NII2'

rl, mz, :
m1,

m2

jl

j\

j2 - 1

jl

+ j2

jl + j2 - 1

jt -1

-l

j2 - 2

jl-2

+j2- 2

...
74

"

1 ,

,'. '.1,

''.\

~ *

' 1:

Jz:
!
)

lz> m1> m2

:::: (}z) + }z2)>jlm;>J2m2 == (}Z)>jJml )>J2m2 + >Jl m1(}z2>Jzmz) ==

:::: ( + 2)> J1m1 >J2m2 .

,,1

j2

-1

"

{> m1 >12"'2} .
(2jl + 1)(2 +J)
, J:

::::

L.L(j\
ml

j2 ) 2!J )>Jl m lq> m2'

mz

75

j2

IJ

l 2

) :

- . "'- '
, , :
,

~2

S .

(. .

=~l, + 1712;, - j~l;s;l-:;, +J2

7.7.

l1 I1

'

'

, ,
-

M s = +1,

7.2):

81,1(1, 2) = a(1)a(2).

.~ . ~

'
(7.16)

,
~ ):

(. 7.1).
,
,

, m . ,

,,' " , 1

, :

ts

=1/2

-'-1/2

'~, .

~ .

s = 1/2, ':;
'

. 81 1(1,

S_

= Sl_ + S2-,

2)

+ S2_)a (l) (2) ==

= (sl_a(Ia (2) + (1) (S2_a (2 = ~(I)a(2) + a(1)~(2).
S_8 I,I(1, 2) = S_a(l)a(2) =

(7.13)

(Sl_

(7.14) .!

1, -,!
.

() ,'

"

81, (1, 2) =

, q>ml q>mz, '

~(1)~(2)

(Ms =

(7.17)

(7.17),
- (7.15):

a(I)~(2)(Ms= );
~(I)a(2)

+ ~(1)a(1);' '"

8.1 -1(1, 2) M s =-1

,

(Ms = +1);

(1)(2)

.1 [a(I)~(2)

);
~

(7.15)"

(Ms = -1).

81, -1 (1, 2) :::: ~(1)~(2).

S = , 80; 0(1, 2) ,
, 80,0(1, 2) or 81,0(1, 2):

s
2,5
2,0

80,0(1, 2) =
1,5
.

1,0

7.3

1
.J2
[(1)2) -

~(I)a(I)].

0,5

(2S + 1)

S; ,
Z.
' n1.
S= , .
ubl. S = 1 (h )

76

7.1.

77

.J/81/2, 1/2,1 =(8-8+ + sz + 8;). ~ [2(l)(2)() - (I) (2)() -

7,

Ms

00,0(1, 2)

1
= .J2
[(1)(2) -

01,1(1, 2)

+I

p(l)a(l)]

-1

01, -1 (1, 2)

= a(l)a(2)

= P(1)j3(2)

(7.15).
r<.
S: 3/2 1/2. Ms = 3/2 (!;

6f2, 3{2

=(l)(2)()

=~ ~ [2(l)(2)(3) 4,,6

J/8 1/2, 1/2, 2 = (8-8+ + .sz+8;) ~[(1)(2)()-

_ (1),,(2),,(3)] = s { ~ [,,(I)2(3)- "(1)"(2)a(3)! +

+.!._l [a(1)p(2)a(3) -

.
P(1)ci(2)a(3)] =

= ~.!.[(1)(2)() -

p(1)a(2)a(3)] =

4.J2;

=13 [ (l)a (2) (3) + a(l)p (2)(3) + p(1)a(2)a(3)].

M s = 1/2

a(l)p (2)(3) -

-(I)(2)(3) - (I)(2)(3)],

2J2

_ (I)(2)(3)]

+.!. _1 [(I)(2)() - p(1)a(2)a(3)] +

, 83/2,3/2 ,

83/2,1/2

_ p(1)a(2)a(3)] + .!. _1 [2(l)(2)(3) - a(l)p (2)(3) 4~

-(I)(2)(3)] = ~(~ + 1)~ [2(l)(2) (3)-

unu. ,

meml~le )

8- { ~ [2O:(I)a(2)a~~) '- 'a(1)a(2)a(3) -

_ (l)(2)()] } + ~ ~ [2O:(I)a(2)P(3)-:(1~~ (7)(3) -

01,0(1,2) = .J2 [a(l)p(2) + p(1)a(I)]~

_ p(1)a(2)a(3)] =

8 s ,Ms(1,2)

). , ,

83/2,1/2 81/2,1/2'
, , ,
:

42

= .!. (.

.!. + 11.!. [a(1)p(2)a(3)- (I)(2)(3)].

212

)2

..
- 1/2

s-

..

'

.
81/2,1/2,1

1
=~
[2(l)(2)() -

(l)(2) (3) - (1)(2)(3)]

(7.18)

81/2,1/2,2

= .J2 [a(1)p(2)a(3) -

81/2, 1/2, 2

= ~ [(1)(2)() - (I)(2)()],

, ~

(I)(2)(3)],

(7.19)

,
~ +1/2:

~2

S ,

1/2(1/2 + 1) =

81/2,1/2,2

.1 [(1)(2)

(I)(2)](3).

3/4:
79

78

7.2.

1-3 -i

0N

s,

= (s +1. 1.

, k

2 2

_1.2 .!.\S
, ~8,
N~i ,1' a(N) +.
2
) s+2:' M~2:' k..

1 I\SMj0N~I' ,~(N)"
+( s+ -12 -122
+--2
,1
1 '1""
'
S+2,M~,k " . '
(k

= 1,

','

2, ... , jN-/),
s+-

~N

+(
01/2,1/2,2

= J6 [2a(l)a(2)~(3) -

1 1
S
-+'
'
2
(

'2

,. 01/2; 1/2, 1 I1

"

. , 81/2, 1/2, 1

(S

= 1/2
S

=3/2

. '~

, - .

J2

m21 J,

~(N)

= 1,2, ... ,jN-n

1 1\

- '2

'2 s )

= -

1 1
1 1\
'1
+"2 "2 +"2 - '2 s ) =

S,-ft{ +1
2S + 2 '

S + +1
2S

+2

(s--lS) " v ;}<

(s-H M+i -i\S)" ~S;:.

(. 7.2). S = 1/2
(S = , S
1) ,

'

(7.20)

. ,

N
2. , S
N 3 (l 2),
).
.

) s-"2' +2:' k

a(N)+

-
i:>:'
", ,
.

, 81/2, 1/2, 2 -

2, k

s-2:

~(3), +1/2.

+1/2 M s
1/2.

1. +1 _.!.\s 10 N -t"

2 2

(k

= 3/2

81/2, 1/2, 2,

S -1.

a(I)~(2)a(3) - ~(I)a(2)a(3)].

COOTBe'FCTByeT ,

Ms

N
=(s-.!.2 1.2 -1.2 .!.,\s
18
-i
2
) s-'2'

0 s, , k

,
~ .

~OMeOB.
. - ,

7.8.

1 11

1 1
S+2 -2 -'" 2 -S
2
,,'

N-

K :

1, (
TOB~e s ~ 1/2). :
] = 1+
J :

s.

81
80

= 1 1/2. S- (1 = )

= 1/2.
, ::
. ri
, Ii

-~r 1I:.~~:
-
,
,,

so

' nFf-m ,

Hso ~ ~]; ~ ~(i.s. + i ,s, + i,s,) ~ ~ <i.s- + i_ S.) + i,s,

~

KOHCTam<l

- , !

V(r)
,

:;
i

I N~>

1 I \) I I I I PoJ3> 1 I \) 1 I P-I~>

I Ptfx)

3/2

I P1P)

1/2

I }

1/2

3/2

1/2

1/2

-1/2

-1/2

-3/2

.!.~

--~

1
2

-~

-~

J2~

~2

1;

~,

- .,.
.

- .

I )

-1/2

I _\)

-1/2

I lP)

-3/2

' . l' ii, , Hso

J2~

.!.~

Hso
( = , 13) (7.12), (7.13) ,

=
-l :

2
1
--~
2

1.

0\

=(~~]. 02 =(~-;) = (~_01) -

S;

= 2"0j;

~~~~~~~~;:~~~~~;~:::~ ;:~~;:V:~~~~~~I~~~~~~~~:;:~::
~2

3..

lx

1+

l 1= 1.
.2

, ,

(. 7.4). ,

Hso

,2(, <).

1+ 1_,

4 1 1+ .

5: c~

1/2 , -

(~)-

, s

,
Z
- ((S(7.20)),
6
_ 1/2
.
)
- , '. ,
:
= )
Ms = 1/2); ) ~ (S
.

: fI ' = + m '

: j = 3/2 +O,5~, j = 1/2

82

-.;.

r< .

(
), -
V(r).

.. .

. ,

V(r)

,
,
,

"

: I;I0H!,I j
,

' V(/- _/).

.
P~.

lj - '2 , '
.
'
.'
i , ~

- ~J

fI

, .

:

[1 (
- 2 ~ r
2

) .

(.

+ sin Sl

1]
+ sin <2 =
2

112 1 ( 2 )' 12
=- 2 ~ , + 2 2

,
, :

2 ,

~2

R=

mll1 +2~
l +2

'

~2

a'Jf)

1 ( r 2 - . +--+V()\jf=IjI.
1 \jf
-2
-2
2

'

lz

(8.1)

-2 1 ( r 2
=----

2 , 2

1
- ) +--+V(r),
2

(. .

=1 +2; = ,/2

l +2

, ~

-- _

7).

lz

\jf

\jI(r,

, <) =

R(r)Yim(e,

<).

(8.2)

- - - 2 + V(r).

( r.) =() (-)

1, 2
\jI r , 84

R(r).

(8.3)

85

 (8.2) ~

, ,

Z4

Y(r).
r I,'~

, ~

, ~

Z2 e4 m 1

, !

V(r) (8.3)

~~(2
dR)_. l(l +l)R + .2 [ + Ze
~2 dr

2
r

Z -

]R

E/I=-~n2'

',~

. . . '

= '

HOBbJe

(8.6)

~ , aToMH~IX -

(84

.. i

, O{J

==

22

== 0,529177

. : "

::, i~
; (~)

" =- 2n 2 '

r
=-;
O{J

Ii

1 .'=-2 =-=27,211 .

EO{J

==-2-'

~ , :

00

JRn,(r)r dr == 1.
2

' ],

,:\

(8.4)

.l~(p2dR)_I(l + 1) R + 2( + Z)R = .
2

dp

dp .

(8.5)

(8.5),'

le , n I. . .. ,

,' 'If(r, , <) ~I9

:

'If~l(r, , <) == N"/p1e- ZP / n ';/(2Z j n)l/m(e, <):

(8.7)

(8.7) .
n == 1, 2, 3:
.
.

, . :

Rn,(p)

Nn,p'e- Zp / n ~+i(2Zjn).

n -

1,2, ... ; Nn,

N nl == [(2Zjn)2/+3(n -1-1) !j(n + 1) J 2n]1/2,

~il(2Zjn)

87
86

R
2,0

R
1

0,10

, ..

.8.1. 1s
)

; n , l - -:

;:. - . <;

11,

E:iHToBoe l 1 = , 1, 2, ... , n -:- 1. -)'

n Io n 2 ::. -'

. - '
s, , d, j ... :

1 = , 1, 2, 3, ... .

ls (. 8.1); 2s = 2 .. (. 8.2).
1s 2s:
r < 2 . .. , r > 2 . . _

'

;
;
(

~ (. 8.3). R (r) - .

8.3.

3s (1),

(2), 3d (3)

) .
,

. ,

= ,

),

~ v.
tI
. , ~
(, , <)

2p

~Jra j ;II6 2- 2s-

.
,

r .

1. n. R(r) n = 11 - - 1.
2. r = s- ,
; .
3. r -'t 00 R(r) .

<,
.
dr:

dw(r)

= R;/r)r 2dr = Pn~(r)dr.

PnZ(r) = Rn/(r)r.
2, .s, 3, 3d . 8.4, 8.5.

ls, 2s,

PnZ<r) -

(
~) ~

' .

, . .
. 8.2. 1s(1), 2s (2), 2 (3)

88

4.

10

12

. :

e-Zr/ n , n

89

3 : Is, 2s, s:.;s.

~

4:

0,6

5.

(v(r) == --;: )
1

2-; 2J /2 .

0,1

10

15

, . .

. 8.4.~~ 2)2 1s (1), 2s (2), 2 (.~j

"7
0,12
2

0,10
0,08
0,06
0,04
0,02

10

15

25

20

, ..

. 8.5. 2 )2 s (1), 3 (2), 3d (3) i

, ,

I;l .
~

90

_:. ( 2:1)

1.

1-

2.

{:

1 ..!.2 (.
.J2
.1- 2"1 r ) ; 2-

r .

<1'0,

. ,
(9.1)

,
'.

',

(').

,
,

, .;.i

. ..;;

- . .
Il . , :
'

.
,

.
(')
: (') :

() =

0' (. . , )

(9.1)
(
) .

'. , '.
.

'1' ( ),

= (') =

f'P* H'Yd't,

(9.2)

() , :

. , = (') - -,
, U (

).

'1' .

'
' fI . -

'

,,

= ('} J'Y* H\Pd't.

' ' ~o'P ri
,
, ':

= J(' + 0'1')* jj (' + o'P)d't -' J'* H'P~~ = J'* H'Pd't +

J
J
J
";' J'* Ho'Pd1: + J8'* H'Pd1:.

+! '* H'Pd't + '* Hc'Pd't + 8'* H8'Pd1: - J* H'P.d't ""

(') =IJn/ n ~ Ilcn / Eo=EoI/cn l =

2

= f 8J* H'Pd1: + (J 0'1'* H'Pd1:) *

(') ~ .

(9.3)

. (9.3)
, '1' -

92

'1'*,

'1',

ip,

, ..:

'1'*.

'

(. .

1), . .

93

, ~ ,

'1'* ~
' ,
.~

'(') = o'f'* wd't - o'P*'Pd't = 0'1'* ( - E)'Pd't = .

= .

i=1

l j1.

'1

paccMO'FpeH iI.

, ,
,

( ).

'(') = '1'* Ho'Pd't - 'P*o'Pd't ,;, J'P*(H - E)o'Pd't =

Ix ,: , -

(J O'P~(H - E)'Pd't)* = ,

n"u

(9.5).
l Oll ( ). ~
I9 , HeKOTopH~

, :
'1' =

'1' = LCiXi,

(9.j)j

, , ;!

Xi:

. ~
, : '1' HOBOroi

(9.4:;

,
}j
./I 'r* ~
- 1lI: (9.4),9 ,
]) f* : :
~

(-- )'

,-\

Sij:

Sij = X7X j d't.

Q t Q~~
:

+ C2e-2,

l, 2 ~(! ; l, 2 ~ .
'1'
, . 1'

2, l, (2) ,
, 1' 2, l, (2)

.
(i = 1, 2, ... , ), -

L (Hij - ESij)C

= .

(9.6)

j=1

! = , ! = , ! = , ! = .

,2

~ l;>

, , , ;:-,
J!: -'

,..!

(Hll -)l + (H 12 -ES12 )C2+ ... +(H1M -ES1M)CM =0,

(H21 -S21 )l + (22 -)2+"'+(2 -ES2M )CM =0,

, ~

94

95

 ,
, i
,

( . -

;):

',

(2 , ( ,

( ).

('2 - ES'2)

(1

(22 - )

ES1 )

-ES1M )

=.

(2 - S2 )

(2 - ESM2 )

(9.7

( -)

(9.7) . ~
.

(9.7),

- ~

, ; ("

... ,

I : ~

). j

(9.6),

yj

{},

'I

'J

= L..CilXi'

(9.6) .
;

.
'I:

i=l j=l

.. i

,
.
n

=L..CinXi'
i=l

JI :

96

(
) .

fj: IJI

C12

= [ ~~: ~~~

...

...

;:~].

, i :
.
'
.. (
'
)
,

L.. L.. Ci~SijCjI = 1.

:::;

'

Cl1

.
, " 2 , ...
~
,. :
6, ! :::; Erar , ~:::; '5. , ... ,

d: HOPMflpOBIO,I

i=1

'n

= ,

oqHOBHoro

("

)
ES2,)

:....

Xi

'n:

'

'( - ESij)1 = ,

(HI1

'n n.

'

.
, r

(
90).
~ .
..'
. .

~ . i1-

, ,

, 1 2

,
, ( -
) ByxaTOMH~ .

rt

97

 , . 1 2
. . :

~ I:2
' (9.8) ,

[~;~ i~J
Ie ; EI,
. , , :J
{') 21 = 12 . . (9.6)

{ 12 ! + (22

= ,

- )2

(9.8~,

= .

'(HI1

, ! == -2; !

'.

(22 -)

r"(':

. '1""

'. .

-fXtX2d't
+ f X~x;dt- JX~X2d't).'; .!. (1- + -1) = .
..
.... '
,2
1,','

"

i .r 'l':: ~ , .,
.: ' 1 'F 2 " ro.;[::

)(22 :- ) - (I2 )2 =

,ff"

( -1- 1122) + Hl1H 22 - (I2 )2 = .

= 2 -

f'Pi'P 2d't =''2} (1'+ 2)*(l -X2)d't = '2(f xiXtd't-

1.

= .fi; 2 =- .fi'

'1 ''I{~Q:

(HI1

12 .

) 12

1 2

= H I1 -

(Hi1 - H I1 + I2 )l + 122 =

(11 ~ )1 + 12 2

J2'

[ + c~= 1 r, 1 = 2 =

:',

1, 2 ==

H lI

22 + (H I1 +22
+H
2
2

:::: 1I +22
11

.'

2'

J' -11 22 '.+ 212--

2'

(H -H22
2
I1

J+?2'

q , Hll.~ 22 ,
1 ; 2 =

(9.9)1
,~

f
~

H I1 12

"-' 12 )1

+ 122 :t:

~ :

J
riat~, -1
~iJ: coorBeTcTByeT 1 = HI1 + 12 ~
J1 J,30 (9.8), -!l
.' (1 '1- 11

t 2 , -

. ,

....

, . ,

"

98

2'

99

 l:i
(~ , I ,

H lI ---<

):

H lI - - - {

.~

-10

-6

9.1. :

- H ll =

22 ;

- H Il

,
~i-r ,

; 22

m , ro,
.
, ,
() ,
,

. 9.1 (. 9.2) .. ,;,\.

,"
P'I:lc. 9.. 3 m
! 2 ' , , . .

I~~l?. (

, ~i~, Xi ).

(-24,11) l' . 9.1.

9.1,

.
H l1 22
, !

Xz
, ! 2 ,
.
!2
. !2 ,
,
.

, H l1 i:- 22

J.

-4
-6
-14 "

(9.9);

9.1,

).

. 9.4ridir:
! I:i '1'2
'1'2'

l (;~~ uz

II

c~.

~.. (;:-9,5~4). :;()l;[ (IO

.

9.1.

, ; .
r: lJ

: (

)
, ., .

.

IJ, ; .

9.1,

, IQ -;

-5

-10
,

9.1

'

100

/N

0/1

-24,114

0,867

0,195

0,458

0/2

-9,554

-0,477

0,594

0,649

0/

-5,331

0,146

0,781

-0,608

-15
-20
-25
. 9.2. ~

101

9.2

"

-12

-19,385
-8,615

0,828
0,561

"

'\
' 2

0,561
-,828
,

:
'\
' 2

-9,010
-11,463

0,050
-1,047

0,984
0,360

-16 -5 )
[ -5 -12
l

'

. 9.3. I !

( l, 2)

, )1

;;
(.

(9.6.

1, 2

:'1

1. ll + 22 2"

2H12 S12+

1- S?2
-

11

ll 22
2

(1- S12)

12

+ 22 - 2H12 S 12
2(1- S?2)

( S12
. 9.2.

= 0,3).

,
,

:. ,

, .

,1

. .
. -~, ,

Cj.,

2'

(1- S12)

. -,
,

-15,8

-16,0

.. 8 m ' . ,
ls R 1s(r) =

"'

"

= 2- ( ).

-16,2

( . ) -1/2.
ls

-16,4
-16,6
-0,50 -0,48 -0,46
.

102

9.4.

-0,44 -0-12
i

~
( l)

, ;

N -

103

 ( )

() , 9
, , .

R(a,r)= Ne- ar2 ,

~
1 ('2)
=--r - +'1-2- -1
,
2 1

2r
r.
"

, :

.
'

..,

(9.10)'
:

ls(1 = ) , ,' ~
Q Il ,

-f2n;...22dx

= _!j R(~, r)~~(r2

R(~,
2
2

-l'
,
- f ":"R2(~, r)r 2dr =
r

f (~, r)r 2dr

N2 =

(9.10).

..

2r

82 / ,
3 2

= 8/(9n)

(mi) = -~ = -0,424 ..

.,

3n

f xne"'axdx; = ~. .

= -1
2'

(i)

= N2 f - 2 d = 1.

dx

- 3
(2
E=2a-2~--;-.

'

r2x2

..

..

(r > , n = 1, 2, ... ) ,

2n +! r 2n+!

-f, -

r) ]r 2dr-

( r 2 R(~",r]"
=--21 [-fR(~, r).dr+2fR2(~, r)rdr.

= 1 3, 5... (2n -1) "I/n

(9; 11?,

n+l

= 2~, n = 2, 1/(4~3Y~
, ~ N = 2~3/2. ~
paBeHcI~y (9.19), -,
l1
, q
,

.<:(. = 2,013 ,
- 13,6 . ~, r)

0,076
,

r)

(.

9.5)

, -

R
2,0

(9.11),

=!(~2
- 2~) .
2
~
, ~, -

: ~(min) = 1, (i)

= -1/2 (. .).

4 "

..

, '::l

". 9.5. ls ( )

, . ,

(, )

104

105

 (9.13) (9.12),

, wf

",

> 1. ~

( +W)('~) +'~) +2'~2) + ... ) =

, ! .

lI. G~~ :f.:r .

;:r :

'

'1

=(E~O) + ~l) + 2E~2) + ...)('P~o) + 'P~l) + i 2'P~2) + ...).

:~

, coJ,

c~eHHe ( ~
W - . '.
j
, , le ~

(9.14)
(9.15)

I9 , , !
r *. ~'i
W ,
. , .

~
, ',

; :

'i

o'P~O) = E~O)'P~o).1

, BBO~T HaJ

'P~2) + W'P~l) = E~O)'P~2) + E~l)'P~l) + E~2)'P~O) .

. (9.16)

(9.14), (9.15). lI
.

(9.15) . ,, , -

E~O) . YMHO~M Yl' ('P~O*

JI .. ~, ';\1'0 ~J?,qIf ~J?

l'

,:

, - , !

, () ~

. , ;]
~
j

"1
.. ~

' n = n' n ,

(9.1i~!,j

. .

n = E~O) +~l) +2~2)

+ ... ,

'P~O)
:'~),

E~l)

= f ('P~O*W'P~O)d't= Wnn

,
(9I.U

, )

'P~)

' n = 'P~O) + 'P~l) + 2'~2) + .. .

,' :

J'P:'P~O)d't = 1;
'n

. , 'P~I),

'P~2), .... ~o).

106

, k = n
. 'P~I)
.

107

 . (\{'~O*

t<: Jj .'d:
, , :tR
ir .

Win+cf') E/~)

: i

.
, .. '
' ! Ir
,'~,

cf') E~O).

:;=

\{'i~) =

~..

"

"

,,1

L Ckm \{'~2)
k=1

(1) _

Win

()

()

(9.21)~ ri
'
',:.
,

.
,

n -~'E(O)
n

\{' = \{'() + ~,
n

\{'j~) -

+ Wnn,

w'n

.... (). ()
/
.
/

\{'()
k'

(9.17~

!
)
... (w"k - ; Onk )Ckm ,
~

(9.17) iC
. , J

k=1

f (\{'~~.* (;()

)\{'~I)d't = (\{' * (/)

Jj o)\{'~~)d't = .

, \{'}2) (k = 1, 2, ... , f)
Ei(O).
. . J
. .
\,

L (W,; - EP)O/i ); = ,
i=1

.
, ,

E(I)

nl'

E(I)

n2"'"

E(l)

n!' . .

E~O). ,
:
( ).

. .

wr

<

"

!- : E~O),
()

()

()

\{'I , \{'2 , ... , \{'!

108

....

.1

( : n). 7

1.

V(x) =

109

2. ,

CI<OM ,

\,

\: ,IP .

'\

. ,~., .

10

_>'

"

3. , TP~Te~o
. '
"
'. 4. ,~~~t
, n + dx 4
5. .
.

B~

n = 2.
6. ~ , !., . ls.
'
7.
.

. '

'...

'

",!, "

, I< t

".

'

W(x, t): = + W(x, t),

i/i

'(,
!

t)

= ( + W(x,

t'P(x, t).

(10

(1.l) -

! jj :

"

'(, t)=I,(t)~~(, t) ~ I,(t)<~()-ikt/li.

, k

' .. k

ij;i (10:1);

'L [dak'(t) <p~ (x)e- ik ( (11 :"-(i", /n)ak(t)<p2 (x)e-ikl /h] =

dt

"

: : : 'L[ Ekak (t)<p2 (x)e-ik(/h +W(x, t)ak(t)<p2(x)e-fEkl / nJ

k

i/i'L dak(t) <p2(x)e-ikl/h = 'LW(x, t)ak(t)<p2(x)e- iEk1 / h.

k
dt.
k ,
.

(10.2)

(<p~(x)e-iml/Ii)*

?J'

da~t(t) =

-* t>k(t)J
=

am(t):

<p~(x)*W(x, t)<p2(x)dxe- i (k -m )l/h ='

_.!.- I, ak(t)Wmk (t)eiIJJmk / ,

/i

(10.2)

(10.3)

Wmk(t) ~ ~; k =

= ( - Ek)!/i

111

l (10.3) ~(
, ~ .;

.( , ,

, ~ l
,

ak = ()
k + a(l)
k + (2)
k + ...

a~)('t) ( ),

~ ,

ag)(1). ()

(~ri,
i ~ k, ~ k ~ ;
). ,
, , Wmi(t) .
. , ,

1 (10.3)

al:):

Ej ,
'j(, t), , , ak(t = )
0kj. (),

da(O)
_k_,

'i(' t) ,
k;f:. i .

=0

dt
da(r+l)
_k_ =
dt

'

_!..1i I.a(r)W:
k(t)eiO>mk t

(10.4)

Ei ,

= 0ki'

m) :

da~)(t)
dt

*J

Wmj (t)eiOOm;f dt = -

/ak{t

= 00)/2)

(, , j>~ ljeKOTOpble ,
, , ,

( :#: i)

a~) (1) = a~) (t = ) -

k:#: i, /ak(t)/2

, , J!. '
( 1) ft (
i: ,

= _!..W: .(t)eiO>mi t .

1i

,
t = : W(t) = t <.
ak(t)

. QI

,

\Pix, (), . . ak(t = )

*J

Wmj (t)ejooit dt.

, l:lI ).
, /am(t = 00/)/2 (Pim )

m.

(10.5)

a~)

(10.4):

;;)

t = -

. (-i t-

h Wmi (t)e/ OOmit + t; )2

l
t

W mk (t)e/ OJkt W ki (t')eiOJkit' dt'.

,
m ( :#: i):

112

. Bo~ , !l
,

< t < 't,

- 0 0

+00.

-, :-

113

 . , t1
= i == ( - /.,
,.:
?! :, ~

'
v
.
' . ' 5'"

t
3

."

. . .~

~pe:~~ i~~;,t)'~~rY _.~~. BpeMeIi~

<

't ~Y~

-const,

Yi?1i~ (10.5) t>

'

. ,

't

=-~ VO}eiromitdt = _-..!JL (eiromi't -1) = VO(I- eiromi't)

, ',

- Ei

,:~ pa~Ha
'.'

.' ,(' ). ,~ 2Vo~ [1...,. S(i't)]

l1:-

. ).

V;Z

st 2 ( .'t/.2)
l,

-(Ei- ,)2

10

(lo.:j

/2 .

. iI

( :,

W(t)

'

"'1

= VO(x)cos( t) = VO(x)( e im! +e-imt )/2.

iVO 't . . '1,

=- -

'2

'.

'.

"

J'ro" (

'.Imf

+ e- )dt =
,.

2,' (mi +

0)

'.

( , - )

::: /2 ( (~mi"': 0))/2), II~. 'ylI

10..1. ,J(I~Qcr

, , ?lJ;~,!< fI~r.: ~Q,r (

(10.:8)'61' ' ,,'

"
.
. ".
' 1 :'" ..... , j' . "
... ;
,
: .Ji: I1:,. ( ~

, '

( ~ .
). 1:Q (10..7) ~
,
;r ~'
.
'.

0.:

..

li~:[Sin(Xt)]2 = lim[xt L(xt?/6+ .. :]2 = 1.

,.

:(~~~~ ~ Il

xt -;0

xt

xf -;0

'xt

,
JiQ 2 t 2 (..

JiQ),

.,.

. . ,

BpeMeHHbIX ~,
.
,

= 2Vo {l- cos [(romi - )1:]) = Vo2 sin 2 [(i - )1: /2] .
(i _,?J)2
(~, - )2 /2
(10..81

I\CiK ,, . bePO-1
' n '
.

2
sin (xt) _( in(xt)]2
t------2

tx'
s.

114

f( - ) '

- -vo- [ei(.mmi+ro>t -'. 1,

. + e,(romi-m)f_
..... .. lJ'

Pmi

10.1.

) Ci' ,~Jj't BpeM:eHe~.

(lm (1:)

"

I:1E

. '
: ~

, , , :,

, .

10..1.

, BJIaB .

JiQ 2t 2 ,
r (i"'- ),
.. ( m)t/2 == !if 1t

115

 = 2r./t. , 2r. Vo~J

, , 1

102 :

:~ dN m + dE p(Em)dE

' :

; ,.,~,,' \<~i:~ ~ , .
'niilQ:~J' ~

" .":~;' ' ,

, . . "~ ,{ , "
..~. ','

-j

+00,
(10.9) :

'""

. .
.'.'
,<l.,

-1
01

~J sin 2[(comi - co)t / 2] dco '

[(; _)/2]2
l

) =1iVo n( ) _

----'..L-_ ;

~J sin 2 [(comi - co)t /2] dco '.

=1iVo pn(Em)t _ [(co i - co)t/2]2
1
2

~j\1 ~
. , ,

= (; -

, d

co)t/2,

, d '
,If E~: :
~

.
,
.

, ' . 6
+ dEm '

, . dN = p(Em)dE~,

'

() ,- (. 10.2). 1l
.,'

P(t) = "\' . (t) ==

k.J

'

m r:I,
"
<). d ; ','
<i () . :

, '
() ,
_

Ii-4

= 2r.n Vo2 pn (Bm).

(10.10)

, C~OPOCT , ,

. (10.10) m~

f,4J/~? sin(2 [(; -)2co)t /2] n ( )dE'

;

~ ,
.

, (10.10) - ~
,
.
'

<l ; ( 10.6):

, 1

= (; ~
- ); -oq'
116

117

, m ::::' ; -
. ,..

/( - E ) = sin [( -E;)t/(2h)] = Pmi(t)

2

( - ; )2 t

/2

m il.

t V;?

. t

(. . 10.1) BCOT~

t -7 oq . " , ~ :;J
- . f( - ;) ~
-, . 2:
!

=
':

()

, :

'. , . ~. '
.

W(r,

t)

=-<(, t),

'00

<(,

"

"

,',

t) ==

-?

'

= x;t: ,

J/(x)o(a)dx = /().

(,

t) = cos(cot - 2nf).

( )

(10.11~
(10.8) (10.11), 1

( u '-,
state-to-state);'

1 000
(1 = 10-9 =10-7 = 10 ) 100

(; ). ,
I! , . Q ~9I
, ,rJ~ !>!

(100-101 ). II' , ~,Q

().~ , ,"L'rO ~
' ; 2n / ~rr
. n,"

i~m

2nV;2

:= - ; ;

( - ;).

(10.12)~

,;
!
, , , ~,
, ( ) = ()' (10.10) '

,
Wi~m

2n

=j}IVm;1

Wmi :

,(

t) == -? cos(rot).

J:

10.12) rJI:
Vm;,

(10.15)
2

;).

!II

(10.13)[1

. t Q~
: : EY~
(10.12) ( - ; ):
;i

2n, 12
;~ = 1; Vm; (

- ;

).

,
I~
(10.14)9

> ; (~

=; + ), ,j

118

W(r,

1
'1

-. (10.15)
, ' , '; -
,

.
, . .
.

,
.
-

119

,.. . . :. . ~;

~. Vmi ','

11

~ , ~

ro

(10..15), -1
.~ .I . . ( ~~.'

,.fi) -:

.~. , 1;l!

() < , :4
.

11.1.

oepa'CU

1.

W = V(I- e-k/).

q,1
.

- ,
, . . ,
.

( ).

2. " Z,
. ( ) OCHOBl

- () ,
,
( ,

).

. MOMeH~
'

2pz?
3.
t

= (1- e-

"

e-k(f-T)

(t > ) .
.
u

','

"

Is-

2pz T(k(t - ) 1)
4. t = /2

5.
(

. ?

= -10,0, +10,0; t =

6
..

2pz

J(x) = sin (xt / 2)

2

tl

1, 2, 3).

q, ~
u

. '

I , ri'. IJ :".
11

7.

. - 'I:
(), , n: , '1!r '.

'!J n-t> ,

. 06.'
.

'' , o~

kI )';

130 , ~60/n

. 3600 : ~
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, - ,
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.
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[ -J7

-.J7J
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. 11.1. Otp : 11.2.

121

~ ~ ~Q.

; ~
(. 11.1).
~
( Ka~

. ,.

. '!I

) ~
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~ !f~ !~

, ~

. 1
- . -::

~ ,')) , ~

. BeKj

. : TOlieK .. .

11.2.

,;';nn

'

G~~I Q~ ( ~~

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B~ ). ~1

, , , ... ,, h" " ~,~

n/( . .

<< , '

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1. n. ( /(n, /( u).~

, :"i

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: = . ' "
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1, . .

: ;

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. 'lJ'\,
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.,
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) f ~1

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r(R;) . ~

r.r..

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(), j

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122

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1 2
..
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12

3 ...
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13

n)
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ln

k.

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123

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- 2'
, ~

. n ~
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n6

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:.,

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;
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, .. 1
of: ~

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.

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(.

11.3):

2-o~

, J

1 ---' 2 ; ~,

xz ( ",!

yz. j

, ~

180fi

( 2 ) -;
xz (Jxz) YZ (Jyz). ':
(1

11.3. -

124

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.

yz.

180, ...:-. [
,

, ,

.. l,'I ',.

, ,

CH 2C1 2:
, " " -

'h , ,

QJi

(JyZ

(Jiz

, ,.

. , ]

(JyZ

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, , -
(Jxz. , (JyZ C2 = (Jxz.

11.3. .u

(Jxz

.
(, ~

(Jxz

(Jy<

, (JYZ C2 ,

'.

11.1

- ) (. .. j
) :

, -
. II
(. 11.1).
.

11.1

eTc , ,

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11.1

1)
,
(
);
2) ..,..,.. ;
.

3)

t;~ ~,

4) .
, , . 11.1
,

Hy

C2v'

~ -

125

. 11.4. rm~
..,!<<1 1,2-6'
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). , '

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(R :
.
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': )

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. ,
(11.1) : :

rpd..6i~.IaeT ... . ..:. . MOJJ;1

.\:" , - [PdC12Br2J2- .; . 11.4j

,:I>~ IO ~ 5: "

C2v' ,
: 1800 . l!JQ:
9 Q. I):aK

i1 Q)i <,2) , -

()

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'

(2 ) =

0'0

1
J(cryz ) == .0 1 .0
1

l'

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"0'

(11:1

0.' :3 = :,2"

.1

1
2

',.
'('

'

.'

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5,

4
5

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. .:
'

1.li'

,",'
,

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i .:

/!

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C2v

. :k: ',

xz z~, (), ( 2 ),
(crxJ , f(O'yz) , ;. ,

, ; . ~

.'

Mii

, ~
~ (), (2 ), f(cr xz )' f(cr yz ) ~.

11.1 C2v' , "i(

2vo ',

::Jl r , .,

:.

() ~. [~ ~}1

() ~(~

~]

(2 )

='

-1

i~

,:q

~ "':"" ();
.'
. .. .!I~
, MaTpflll
, .. ('~~
).
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:~

126

( crxJ ( cryz ) ,

(j

.....

~'

, 91
;

"

-1

f(cryz ) =

1.

127

 . , e~

, - s~

2- :

11.4..

[~

() ::::

C2v ~ ;4

~}

( )

J
2

, II' i '
: ( - ), '
1200 ( ), F! 2400 '
(Cj) ,

f(Cl) ::::

:J

(0"1' 0"2,

") (. .

11.5).

.j3

''1

("I)
"

IM . , )
1200,

1200

(0"2)

,!

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2400. ~aJfM ,, . Cj ~

r
u

,j

11,41

0"1

0"2

"

0"1

0"2

"

"

0"1

0"2

Cl

0"2

0"1

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;
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::::

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1
2

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,, ,' fv ,' ,:1,j
, m r C2v MO~
.

~l~

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. 11.2.
, '

128

2
1
2

v .

"

Jj
::::

, ()

2
1
2

Jj

1
2

(").

-'.!
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43

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1

(11.2)

2pz

, 2 2

.
f(R) (11.2) v
,
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,

. (11.2) ~
2- . ,
2-
3- .
(2 3)!I; 5

129

 rp

6 ,

-f!!1

. , ( )

.J3

1
2

2
1
2

,..J3;
2'
( )

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, {.2)
(1l.3},. (11.4) ..
(11.3). '1,f;{1'lA}

: 2/2.,. ':r ,:~

( 'I:I;)
. 1:, (11.2) i iLUbl,
(11.3) (11.4) ntu/;rrtJUlI
, ,'
.
, ~ v

1
2

.J3
2

.J3
2
1
2

";<',1,.

() = (1); ( ) = (1); ( Cj) = (1);:

( = (-1); (2) = .(-1); (cr) = (-1) .

1s- 2S-0 :Q:wrx

, ()~.t;I1~q~i~;~

'~ II~ (:7v ;!>IJ;3:~

, 3d- ~
, KOTop~e, , ~
(11.2). , , HeKOTOPO\~
, .!,

(11.2) - . l
: o~

22, , [

oHi

2 2, 1 1 (1)~
FJur, 2pz' ~

(11.5)

, 9 Ix ~~'I'~.(l1})~ 6t.~
~~ 2p z. Ta~~ Q~q~".II;u;~.1.s,.2~, 2pz
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,
; (11.4).,
f(R) , (11.3)., :..

2 11 2, 6

3dxz , 3dyz , (
). , :'

j: ':

, 2

3dxz ,;JO '

3dyz '-~)
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. , 2

() =(~

,'
. ,

).

; " 'r:t",'
.
:.

j ','.

()
(

130

t :
' - . (11.3).
(11). ::s-
.

'.

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= (1); ); = (1); ( Cj) = (1);

:::; (1); (2) = (1); (cr) =(1).

(11A~

3. v
1 2, (11.1) -

131

. ,
(11.1) 1J :
, eJ:
C3v,'~ (;

.~

l1 'v

). ., " ,:

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, }

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1
1

1
-1

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XCRi ),

(,(R' - I H~

6 .

' . ]j

ix 'fip . ,
;

nu, '
:
.

(11, (12,

(1

~). :II

11.3

1
-1

( )

Tc Is- , SI, S2> S. .11.3

3 '

(11.8)

JIiI :

E}k =m I;r}k(R)R (i, k

h R
'
,

=1, ;.. , )'

',,'
',:,:, : i
(3 1 + 1 . + 1 + 1 1 '+ 1'1 + 1 1) = 1,
1 6
. '. . "
. '
(2) = 6.(3.1 +1 + 1 + 1(~n+ 1 (-1) + 1 (-1
(1) = -

'1
(11.7~

'1

q ,\1I , ~

: , . ~

()

l1.,~ ",
I-j: , )i

. G, I H~
~

,. '_

'

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= -(32+0 (-1)+ 1 (-1)+ 01+ 01 + 01) = 1.

6

SI'
,
:

(11.8~
,

l '

= ,

Q1
~
. - , ,- , Tpex~
. - t. . TO~
, .: 1, 2 ... ( 1 ' 2 ). f,l

""

......

ESl

-2

fll(R)

,..,

,..

=SI, C3S1 = S2' C3S1 = S3, 0'1 S1 = SI, 0'2 S1 = S3' ' Sl = S2'
(11.7)

1,

Efisl

=6(1'SI +1,s2 +1s +1,sl +1s +1s2) =3'(SI +S2 +s).

, . ls-

, o~

g,

(t1g, (2)' ~

rpej
: ' - ; 1t, , ... ~

. , ;1

132

133

 aJI ~
(11.7) : Ma~
rll(R) (11.3),
.'

(11.9)

(),
1' _1

, ;;, --:.
' \ I:l' :

, ' ."

: .

~ (11.8) ,::;
. SI:'

a S1 =~

~1:

, '2(0 ",. +-"-'

J:

',~'
21 S1 = -6

.'

'i

"

".

':5'1

,,\

,2

"

: :

<( )

'

= .J6 (2s1 -

.
S2 - s);.<( )

1
=.j2(S2 -

2'

+0'SI+0'S+'S2)=-:(2'SI-S2-S)'

.j3):J3

,J' , ' ' , ," Jj

~'
S2- - " S3 + '$1 ' - ' _ . S +_. S2 =-' (S2 -S,3
2
.., 2
2
3
'/

...
2
a (R)Rs
LX
1 = -(2 SI -1 S2 -1 S +
R
3
.

"(11.10)

(11.9). ' KoMrioHeH~

,
- , S2:
'1
,
'

(iiI

8).

(11,~

, B~

: (11.11)

, , ., ., Ib, (l1.~,,'"
, , 1200

C;SI

== S2,C;S2

= S,

C;S3

= SI,

--

<( )

.
.

;<( ) =

.1

(S3 - SI) '=

<'( ).

'

~~ .F>"
"

(11,3).

(11.10) (l1.1.1),t
: )!lw

' aSl + ~S2 '+ "(S','

m d ( (11;10):
',

= .J6 (2s2 -S3 -SI)= <'( ),

~ ? ? '

<( ) <( ) :

1( + ~S2 + "(S)(SI + + s)dv = , ,

I(aS + ~S2 + "(s)(2s1 "- S2 .... s.)dv =0.,
S2

i.

, , . 1S-0,
, , = , ~ = 1, "( = -1.

, <( ) =

.j2 (S2

- S3)

, ~ -

~ .

,~ , J<i:l -

!l.

1.

'.

'

2;

134

135

11.5.

11.6.

", o~

,,

ro lIpor "
. ,

fl(~ (3)
.

(3) : (123) (

), (231), (12), (213), (132), (321). Il

, .

(1)(2)(3) -

f~7(R)ih!k(R)dR
,

. , '
"

7.

~2

S ,

S(S + 1)

3 5

= 2 "2

Ms

. , M s =

~'1'

, 'i 'k
,

, .
(. . )
,

= 2'

93/2,1/2

2:

1
= Jj
[a(1)a(2)~(3) + a(1)~(2)a(3) + ~(1)a(2)a(3)],

. :'

:.
93/2, -1/2 93/2, -3/2'
"
'
, -

,:

. ' - i
, ,:! H~
; !

91/2,1/2,1

~i '
, . .
: ,

l
l

. ~
~

W;,k

=f~7(R)~\fk(R)dR.

i1:

= J6 [2a(1)a(2)~(3) -

"
,
(1)(2)() -l)(2)()],,

1 '

91/2,1/2,2

"

= ..fi [(1)(2)() -

"
B(1)a(2)a(3)].

91 92

. P(231) 91:

'
(11.12)1

)~
-j

(11.12) ' ~,
"

,' -1

\f i ' k , KOTOPOM~
-. ~~
, , ";'

P(231) ~[2a(1)a(2)P(3) =

(1)(2)(3) -

p(1)a(2)a(3)]

~[2(2)()(1) - (2)~()(1) - ~(2)a(3)a(1)] =

= ~ [2(1)(2)() +

a(1)p(2)a(3) -

.1 [a(1)~(2)a(3)

(1)(2)(3)] +

(1)(2)()].

..(j

136

137

 ' ~

=-! =_J .. (231)8 1 =-161 - .J3 62. j

2'
2 '
,
"
2
2
~

)(~ . 12). :
(~1) ,

~,

. : (<1>;)

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1
j
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2

r (),

(\jf;) --:- i': (), ,1?,I

tij(P) = (-1)j;().

J]
2
1
2

! ,

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v (

(11.3). , iJ
240 aMM~
(. 11.5) (123) ~ (231).,~

= -L<I>k\jfk
.jJk

. ,
:

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61 62, , ~
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v J

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(11.3) ~ . ~

: ij

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1t(h).

. fI~
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. 11.5.

138

1t(N).

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, \jfj -

, ~
. ~

139

1. , Ta~

J;I. ypo~
2 ?

2.

'

3. , -l f(A)-I.
1
4. 2 ~
. 11.4.

v'

v'

+1

+1

+1

+1

+1

+1

-1

-1

+1

-1

+1

-1

+1

-1

-1

+1

R ................
X(R) ......... +7

C2z
+1

a~

' +5

a YZ
v
+3

12

IIJ

12.1.
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i,

N , 13 'aTOMHb'IX
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) ,
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141

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, (:)':
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Ix '~:.

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. , :"

Jl\",;,nP

I2'(1, 2, ... , N) == '(2, 1, 3, ... , N) == '(1, 2, ... , N).

' , \
-<

, :.
r ~''n:
-, :'FI

" . I

, . :!.

. ';.;yR0

(1928) . (1929). Il'~

I2'(1,2, .. ;, ) =='f(2,1,.; ... , N) = -'(1, 2, ... , N).

:; "[
"
.

()';':0'J'R .

.," -',
(}f) ~. . .,~
nm , : . . ...",;
, . Ji-;,~,
, ';~

'(1, 2, ... , N) =det!'1'!, 'JI.2. '1' .... ,'I'NI.=.

, -:-~

( ),.,;

'1'1 (1) i\j!1 (2)'1'1 (N)

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

, }

\ = i.

Ji, r , Q ,:
(Q ) -:- n-m.

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

'1'!! (Xj, Yj, Zj, (Jj)', G- ~:

: <P~(Xi' Yi'Z;), .:

Xms:

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, ,.(12.2)

'1' N (N)

i,

1j.JNi. - J;I,
. . N!
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, , -

' ,
m'
um.u,'
-- '/(m.
, : "

: . , .

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,"

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. ,!;>! BepHe~ytI ~ ,.,

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, :
; ffmfl.
I;l () ,
.0,-\ (-) .

I2'(I, 2, ... , N) ==

. Q~ -,

. : '.

-:

-; Jl'l. , "::!
()1'.: ,};
, - - .;'

, ,

. .

( , JI I')
-'1'. N~F{~
, ~,i!(~'

tm:Jm, T.~. -'

142

2).

, , ' ,n :

'1'1 (2)
'1'2(2)

JNi. ....

.
'1'N('2)

143

, r, ,r r ;
, , ,'
: .,

, 11

0/.

, ..
r
0/,

: fl,

(12:) .

, CTPOi
. ,
;

, .. Q"~~

': ,',

(JJ ) "

0/

.
,
, -
.

. .I1f1 J;30 ;
, ,J , (
, ,

. Jl ;

. ,

-. i1

.
~

=-I,(-1)Q .
.fiii.

. fI

q-

- 1s2. - 0/1 = 1sa"

0/2 = 1s~, 1s ...,... . ,
<U;I

(),

.
;

0/1(1)0/2(2) ... o/N(N)

(12.2).
,
, Q

,
.: , OCItOBHOM

. fO
::t;, .
t,

; l,\1 .

'(l,

2)

= detlo/ I

0/21

1 10/1 (1) '1'1 (2)1

1 11S(1)a,(l) ls (2)a.(2)1.
'1'2(2) = .fi 1s(1)P(l) 1s(2)~(2)

= .fi 0/2(1)

'(l,

2) =

.1 [ls(1)a,(1)1s(2)~(2) -1s(l)~(1)1s(2)a,(2)]

1
=1s(1)1s(2) .fi
[a(1)p(2) .,.. l),(2)],
.fi[,(1)(2)- (1),(2)] -

Q -

1s(1)1s(2) (
),
.

'(/I, 0/2' /, ... , o/KN) ~ , 1
N - o/l, /, /, ... , o/KN, ,

144

.
l'e ;J .

1s12s l -

145

 , 'l'1

= lsa,

= 2sp.

'l'2

'

(1 2) =
1,

d~tl

I=' ~.')'l'.) (1)

rct1

Ji [~S(I)~(l)2s(2)P (2) - 2s(I)P (1)ls(2)a(2)].

tr~ ~

S = 1, Ms = -1.

'1

'.'

'

.' .

S . li ~ ~
., - 'l'

=dtl\ll \114/ =

' 2 (1, 2)

.1'l'(1) 'l'(2)1

=.fi \114 (1)

1
,,2

1 11S (I)P(1)

'l'4 (2) =

2;

~,

2, . ' .

~ [(I) (2) (l)aj2)] .

,,).,

I(). ()":'
'.

S , i:I ~

Z.
:I1 ' m :
'
.

, .

..1

[ls(I)2s(2) - 2s(I)1s(2)]P (I) (2).

.1

[ls(I)2s(2) - 2s(I)ls(2)],

. (
), ,
~ .

.

- 2s 2 ,
., . -

"
'P(S =O,A(s

=,0) = .fi (' 1

"f:'

' 2 )

= ~ [ls(I)2s(2) + 2s(I)I:5(2)] ~ [(1) (2)~P (l):x(2)],

146

1_

. , .:
~2

.fi

.,.

'P1(l, 2)
' 2 (1, 2),
1

~ [ls(I)2s(2) -2s(I)1s(2)]a(l)a(2);

"

1 11S (I)a(l) Is(2)<X(2) 1

2s(l)a(1) 2s(2)a(2~ =

=+1) = det 1'l'2 \11/ = .fi

.fi (' 1 '2) = .fi [ls(1)2s(2) + 2s(1)ls(2)]

=1,' Ms =+1

'.,
'.
1 !IS(I)P(1) Is(2)P (2)
'P(S = I,Ms = -1) det I'l'l 'l'41= .fi 2s(1)P(I) 2S(2)P(2~-

= ~ [ls(I)P(I)2s(2)a(2) - 2s(I)<X(I)ls(2)P (2)].

= IsP, \114 = 2sq

ls(2)P(2)
2s(2)a(2) =

.fi 2s(1)a(l)

'P(S = 1, M s

"~

, t) , ' I (1,

'

; , ~
.

mi )
",2'

) == .1(~l +'' 2 ) =,

m
, ,

. ii"

'.

!:::

[ls(I)2s(2) - 2s(I)ls(2)] ~ [(I)(2) + (1)< (2)] .

.fi
,,2,
,

=-

' I(1~ 2) =

'P(S= 1, M s

~)IS(I)<X(I) ls.(2)a(2). ~
.fi 2s(1)P(1) 2s(2)P(2)'~

'l'1(2) =
'l'1 'l'2 .' ."fi 0/2(1) 'l'2(2)

''l, 2)=

'1

Is 2):

[2s(l)a(1)2s(2)P(2) - 2s(1)P(I)2s(2)a(2)]

= 2s(I)2s(2)

.1 [(I)(2)

(I)(2)].
147

 s-, Bce~

paBe~

. ,

's, )

1s2, Is'2s', 2 s 2 : ,

',

= 'I"('S,

Ji

82

,8z

(S = 3/2, Ms = 1/2).

1~2) ~ IS(1)1,~(2)~ [(I)(2) - (I)(2)],

. ,
,
,

'I' 2 = 'I"('S, Is2s):::::[1s(I)2s(2)+2s(1)ls (2)]_1 [ (1)13 (2) ,

, .:',
.fi

'I' = 'I"('S,

2s

,
1 2 .

(1)(2)],

= 2S(I)2S(2)~ [(1)J3(2) - J3(1)(2)].

(12.4)-

, :

~ '

( , ,

" ~.,
IS ~

,
).
1 2 (12.4) .

'I'('S) = 1 ', + 2 ' 2 + 'I' 3.

(l,Q
, J;I

'1, '2, 'I':

"

Ai -J

. OCHOB-i

1s22s ~u;'
1

.,

. 1 { 1.

.'

'I'N(1, 2, ... , 7)

12.2.

= detj1sa IsJ3 2sa 2sJ3 2_l 2 2p+lal.

,
. ,
,

~ [a(1)J3(2)a(3)-J3(l)(2)(3)]' .

( ), . .

..-

- .fi [ls(I)2s(2)1s(3) - 2s(1)ls(2)ls(3)]x

.

:

(12.4)
!

148

, "

",2

~ [2(l)(2)J(3) "'-(1)J3(2)(3)-l)(2)(3) ]}.

,
(. .
11). ,

.

'I'Li(l, 2,3)= .fi,;[2(1S(I)IS(2)2S(3-IS(l)2S(2)IS(3)-2s(1)ls(2)ls(3)]

f .

(KBapTeTHor.o)

; f ;

:
..

3). . () , ;
l>IX

, .

ls(l)a(l)

Is(I)J3(I) 2s(l)a(1)
' (1,2, 3) == / Is(2)a(2) Is(2)J3(2) 2s(2)a(2) .
",6 ls(3)a(3) Is(3)J3(3) 2s(3)a(3)

;, , '(1, 2,

H'I'

= E'I'.
14Q

 KOM~

'1

S ::,,'(RS) = (!).
, R' ~

':

j)j

R' = 1 '.
'j
. , ' OHO~

::: '.

,!

/- R' ;

; ' 1 , ";
() ' , . . ::;
'1, \1/2> "', '/ rr j-Mepl
tl: r :!

d 1 2 t

Gc {<l, <2> , <} {\jIl' \jI2, .. , \jIn}.

n <J'j\jli {<p\\jI!, <P2\j12' ... , <J'm\jln}.

, , ':"
, "
.
, i

G .
(11.6). ,
Xr(RJ :
1) 1 2 - I , I

Xr(R;) == , (Rj )Xrz (R;);

2) 1 2

, ,
, j
. ' ; ' ,

::. cm

R Qh' : ,~-

<;

Sij

tij

R = IR~I ~, ." R~fl =trl/(Ilitr'J(R),.:! r,,,(R)I~I~J ... iJ!",1,

\jIj (Xl)<J'j(X2)].

: si) ti} S ,

tij -

Si}

tij'

, !'

lI,
:

X(S; R,.)

= kx~, (R

j )

+~

, (),

' .

g ''::: de,t!<J';<J'j.:.<J';"I'He
:'' , . . >
. <pj.
.
, ',.
TO~KO , -

.J2 [<J'j (! )\jIj (2) + \jIj (! )<J'j (2 )],

= J2 [<J'j(x!)\jIj (2) -

\,

., :

'

= \jIJ.L = I,r/1i(R)<pj,
;=\

: :

...1

R<J'j

'

[t

Q:

R<J'2 '" R<p/ ==

~

i=J

j=1

=!

I, (R) I, 2j (R) ... I, / (R)( -l)q Q \.<J'J

(-l)q

,.

R =IR<P!

<2 '., <J'/

(R)r 2j (R) ... / (R) ] !<J" <2 ... <J'/! =det!r

!=

ij (R)!

=.

( +1 ~ -1).

~ :.

(; Ri ) =~~,(Ri)-~,(R?).
150

151

. J

+1/2 -1/2 @
,

"

~ .

13

.'

f , J
/, ]

. aTOMa~
~ : ~

.~ (, , :-1
, ) aTOMH~
n / ~1

. 12, :t

. ;
, , !i.~{(~J:>

, . . 0 9 ,' :'J

(2/ + 1).

- , ~

, , -j

. t;'~.

( -J,
1 A 1g). -,i

, l>I :r
.

TblX , , ~J
, A1 -~

j
, . :

(1 )

A
== 2:, -- /:;,.; - 2:, 2:,+

, -!
.

,,'

,.

;=1

Ng

=l ;=1 riA

1
!-.
.

I<j rij

~,130: . ;

. ,t(~~,

1. ~ . i
2. -"
( 1s 1 2s 1 s 1 ).

. -;

''

C2v (. . 11), '

(13.1)

) (1 al)2(2al)2( l1)2(l)2(lz) l(4al)l;

) (lal)2(2al)2(lb1) I( 2 (l 2 )2(4al)l.

, '
.

bI:;
N :
.,' .

'", - ; ij - ; (13.1).
v

. '(1, 2, ... , N) - ,

q -

P'P(l, 2, ... , N) ==(-l)Q'(l, 2, ... , N),

; (l, 2, ... , N) -

( , ;' ,

N -). ' .

.
1"~

"

j*(1, 2~.;., N)F!(I, 2, "', N)d~=

f-

1 L(-l)q *(I, 2, ... , N)F'f!(l, 2, ... , N)d't,

= ;;
",N!

.~ F

(l,

, :

-
'

; ;, """"",. ; , ~

,
,"~
, ~
~, N*'(l, 2, ... ; N) (I,2, .... , N) ~

S(I,

~~ .

--1 " , , '

_'~

oepaT~pOM ,, . , .. , P'

cl

, ~:

. 'P*(l, 2, ... , N) (-I)q,

--1_
,
(I, 2, ... , N) = (l, 2, ... , N).
.~

=>

1,

2, ... , N) = A'I'I(1)'I'2(2):'.'I'N(2v).
,

I I\ftf1:J
.

, , ~ (~
, ).
~It

JS*(l, 2, ... , N)'P(l, 2, ... , N)dt ='

=..JN!J*(l, 2, ... , N)'P(l, 2, ... , N)d't=

2, ... , N)(p-l F)p-l\f!(l, 2, ... , N)d't =

2, ... , N)~(1, 2, ... , N)d't =

=.JNj:J*(l, 2, ... ")(l, 2, ... , N)dt=

' ,:

,)\\

=L (-l)q J\jIi(l)\jI; (2) ... \jIN (N)Avl (1)\jI2(2) ... 0/N(N")9'tldt2,.:)t,N:/

(fJ)

\\~

(1,2, ... , N)F'f!(I, 2, ... , N)d't =

=JNf *(l,

(I,

= J*(l, 2, .:., N)'P(l, 2, ... , iN),?'f =

k ~(-I)q(-I)q ~*(I,
= JN! ~f

= 'I'1(1)'I'2(2)"~,.'I'~N)~,Ct"

'1' .~I ~,a~9P,

,

2, ... , N) =

k ~(-I)qJ -l *(I,

2, ... , N)

2, ... ,N)~(1, 2, ... , N)d't.

(13.3)

1 'I'~(I)\jIl(l)d't11 'I'2(2)'I'2(2)d't2 1 'I'N(N)'I'N{N)d'tN

-,,1

, ,.'

=1.

1 '1'7 ('I' k (i)d'ti"

f*(I,~, ... , N)F'P(I, 2, .;., N)d't=

1''1'1; (k)'I'/ (k)d'tk'

. , -

=.JNi.f *(I; 2, .. , N)N(I, 2, ... ', N)dt;

(13.2)

, 1'*, 2, ... , N)'P(1, 2, ... , N) d't

.

, I~I .

154

"

Oll .

f hi, ,ll . -

o~epaTopa hl:

155

 P12

fJ*(l, 2, ... ,ij)hl~(l, 2, .... ' N)d't==

==

2: (-1)q f \jft(1)\jf2(2) ... \jf'/v (N)hl 11vl (1)\jf2 (2) ... \jfN (N)d'tl d't2 '"

d'tN

- f f \jfi (1)\jf 2(1)g12 \jf~ (2)\jf] (2)d1:1 d1:2 f ... f \jf'/v (N)\jfN (N)d1: N =
== f f \jfi(I)\jf2 (1)g]2\jf2 (2)\jf1 (2)di1d't2'

, ;

f \jf7(i)\jfk (i)d1: i '

!
' \jf7 (i)\jfk (i)d't;.
,
, . '

"

fJ*(l, 2, ... , N)L,gijJ(I, 2, ... , N)d1:="

i<j

== L,

[J f \jf7 (1)\jf; (1)g]2 \jf} (2)\jf

(2)d1:1 d1:2 -

i<j

jJ*(l, 2, :.'., N)h2J(I,

4, ... ,.N)d1:==h 22

- f f \jf7 (1)\jf j (1)gI2 \jf} (2)\jf; (2)d~ld1:2

J. ,

. ,

,
mu n-m
,'

J (1, 2, ... , N) = (1, 2, ... , N):i: \jf] (1)\jf 2(2) ... \jf N (N),
J'(I,

, () J

. .!

Oll . m

2, ... ,

.,..,'
N)='(1, 2,

':"',."~.'";

~,

... , N)=AIl(1)\jf2(2) ... w'N(N), '

(N - 1) ,
\jf] 11,
-.
.

f'*(l, 2, ... , N)2:gijJ(1, 2, ... , N)d1: ==

:1

i<j

, . .
i

f (J )*Jd1: =
1

l;! , g]2;:

= L, (-I)q Ii (1)\jf2(2) ... \jf'/v (N)P\jf] (1)\jf2 (2) ... \jIN (N)d1:1 d1:2 ... d1:N'

f I \jfi(l)\jfl(1)gI2\jf~(2)\jf2(2)dtld1:2f f \jf'/v (N)\jfN(N)d1:N ==

= fI \jfi (1)\jf] (l)g12 \jf~ (2)\jf2 (2)d1:1 d1:2'
"
156

\jfl

11

f Ii(l)\jfl(l)d1:lf 'I'2(2)'I'2(2)d1:2 ... f'I''/v(NWN(N)d1:N = .

. ,

f (J'(<(II' '1'2, .... , 'I'N *J(\jfI' '1'2, ... , 'I'N)d1: ::::0.

157

~ . , ~

hl;

f ('1'')*(1, 2, .. , N)h1 '1'(1, 2, ... , N) d't =

~
="'""' (-1) qfG'l*/2*(2) ,,;WN (N)h1 P\j!1(1)0/2
(2) ... 0/N (N)d'tl d't2 '"

/ (N)o/N (N)d'tN

j('I"(G'I'
=

h2, h, ... , hN. ~

,,<

"

<2, ... , o/N*(~hl )'1'(0/1' 0/2, ... , WN)d't=O,

,

"

f ('I"(~" ~2, ..., '" ' (~ g, )'1'("'"

=f < (l)h10/1 (1)d't1'

g . ~H.~ . paBH~.:

f ('I"(G'I, <2"", o/N *'1'(0/1,0/2':'" '1if.i)dt,= ,

d'tN

f G't(1)h1o/\.(l)d'tlf 0/2(2)0/2 (2) d't2 '" f

(N - 2) I<: ,
- 0/1, '1'2 G'I, <2'
~ :f '9'-
. ,~~",

=f G'i (1)'1'1 (l)gI2G'Z (2)'1'2 (2)d't1 d't2 I

"'2, "',

'l!N.)~t:~

J G'i (1)'1'2 (1)gI2G'2 (2}'1fl(2)~,~~:.,

\

' ,'

* f'l'*(o/t,o/z, ... , 'l'N)X

x(~k J'I'o/l' 0/2, ... , o/N)d't=

."~

! t
:

f ('I"(G'I, 0/2, ... , o/N

...

1"

1"

"

')

'!1
.
'".
.' ,

, KOT~pbie 0i
:

= f G't (l)h10/1 (1)d'tl'

(ilhli) == f 'l'7(1)h 1\Vj (l)d'tl'

. J

'
1

[ij I k!] ==

f f '1'7 (1)'1' (1)gI2 'I'~ (2)'1'1 (2)d'tl d~2'

j

I' ,

f ('I"(G'1'0/2' ... , o/N *

(~g!i Jq1(0/1'0/2' .. :' o/N )d't =

I<J

J,'I'*('I'i, 0/2, ... , 'l'N>'I'('I'I' '1'2, ... , 'l'N )d~"'71,

N'

= L[J G'i (1)0/1 (1)gI20/7 (1)0// (1)d'tl d't2 "'1=2

J'I'*('I':, '1'2, ... , 'l'N )'I'('I'b' '1'2, ,.. , 'l'N )d't=O,

'

- f G't (1)0/1 (1)gI20/7 (1)0/1 (1)d'tl d't2 ] .

, -1
.

,
m n-

J'I'*('I'i, '1'2' ... , 'l'N) ( ~k '1'(0/1' '1'2, ... , 'l'N )d't;:: ~(ilhli),
N

J '1'* ('1';, '1'2' ... , 'l'N

158

(~hl )'I'('I'b' '1'2, ... , 'l'N )d't=(alhlb),

fI*('I't, '1'2, ... , 'l'N)(Lgij]'I'('I'I, '1'2, ... , 'l'N)d't=I,([iiljj]-[ijlji]),

I<}

i<j

'*('1':, '1'2, ... ,

'l'N>(~gij J'(\jf' '1'2' ... , ;'IIN )d't= ~([ab Ijj]-[aj lib]),

I<J

'1'(1,2, ... , N)=(l, 2, ... , N)=A0/1(1)0/2(2)"'o/N(N),

'1"(1, 2, ... , N) = '(l, 2, ... , N) = AG'1 (1)G'2 (~ ... 0/ N(N),

'1'*('1':,

'I'~, ... , 'l'N )(~g!i J'I'('I'b' o/d, ... , 'l'N )d't=[ablcd]-[adlcd].

'<)

159

1. aTOMH~ ~ : ) 1 ; ) 1 ..,
1 /?
..
2. '~!

(,',

-'- '

-2 L
L;=1 j=1 l';j

(i

* j)

L-,

3. ( ..

H~.

14.1 .. 0

i<j rij

4. :'II i~ , :.
. .

- I,J;e'rkJ: Me;~OOM
. -
: J1

5. , 'VIOO(rl)'VIOO(r2) :al
~ ,
('VIOO(r) -

, .

).

*. , , '
. 1930- .

6. , ~

\ ls<xls~ Ilj1211sa2s~).

,
,-- '
I ;, fI}?I~ ~ :\

'J1 ('). ' ttitJr dJ1!n

61t, t,

, , U-:il-,

, :~'G,~~ :kt
I .
' - :.~

) $ii ggi'
;> . ,J
-

"""''''''I'\DL
~OB, , ;;;"W~->;,..:"f.tV

5 .
, ,
...

lVlvl

V.L~\J

-
,
,

J.
I-1 ,
:,
lI ).
J -

* ~ 1i~8-_'
: ,

2,

161

 ( l;> :'

,'

) ',

, 0'V7'+-
, ,f[ :

,"11

,.

hl'V;(l) +

~ [f 'Vj(2~:j(2) d't2'V;(1) - f 'Vj (2~,;,; ;~)d't2'Vj (1)]N

- Lj;'Vj(l)

'

14.2.

','"

= .

)=1

i 1 , )h

N-

..-,., :'('" 1 Z ,)
1
1
~ l.,.;.-; - 2: --..,' +2:,- = h ; + 2:-.
,[=1
2
=1'
' ;<j '
;=1
i<j '

2:

F'V;(l).,- Lji'V/1 )

, ,Jfe , ~611
~ N .~-:'.
'(1, 2, ... , N)

j=1

F'V; (1) -

=de,tl0/1 0/2 ... 'VNI.

~ t,8

t [f ~j
j=1

'

F'Vi(1)='hl'V;(l) +

~,",J o/j.(2)\~i(2) ~'t,2\iI;r(i)].

(2)\jI) (2) d't2\Vi (1)

'12'
. \ ; , 'i2
"

[f

~ .

"

Fk ;:

'

+ t[J'Vk(1)'V;(1~:j(2)'Vj(2) d't1 d 't2 _,

I'
'

"

Fk ; = 'VU1)~I'V;(1)d't1 +

,,'i2

':; -

'!

(14.1)

':"!

',"

'Vk . ' ii~ :

'i2

,,<

, , .lJ ~

'

2:f
0/7 (1)h10/; (1)d't1 +
;=1

"', . J
o/j(l)o/; (l)\jfj (2)o/j (2 d d' _ 0/7(1)0/i(l),o/j (2)0/; (2 d d
+L
'
',
'"1 '"2
",
,
'"1 '"2
;<j

'

=Q"

_J'Vk (l)'V /l)'Vj (2)'V; (2) d't1 d't2]'

N N

L2: jiJ 'V7(1)'V j(l)d'tj'

(14.2)

'12 ,

;=1 j=1

,, , Q:-,

. \ ."

'VI

(Fk;)* = /! (1)h1'V; (1)di1 +

'= 0'Vi(1)h1'V;(1)d't1 +
+L
j

[f o'Vi(1)'V; (1)'Vj(2)'Vj (2) d'tl d't2 _ f o'Vi (1)'V j 'Vj (2)'V; (2) d't1d't2]'~
2

'12,
N

- L j; f o'Vi'V j(l)d'tl = .
j=1

+L
j

'i2

'i2

=f'V7(1)h1'Vk (1)d't1 +

"'[f 'Vk(1)'V7 (l)o/j (2)'V j (2) d'

+ L.J
j

162

[f O/k (1)'V; (l)'Vj (2)'V) (2) d'tj d't2 _ f'l'k (1)0/j (l)o/j (2/ (2) d'tjd't2 ]~* =

'12

'"1 '"2 -

f'Vk(2)'Vj'(2)'V) (1)'V7 (1) d't d't ] - F

1

2 -

ik

'i2 '

163

h.

, .ti:~

ij . (14.2) ,

" ,

~ . .

14.3.

Tei

[f

~ u";. {;,,~, (1) + ~ '1 (2~ (2) d"'i\I) - [~: (2~, (~) 4T'~~ (l)]}

-
( )

- L L 'ji<l'v (I)UvjUi~ ==

' .'." '

v,i j

-' , ~

= { ;,,~. (1) + ~

[f ~: (2;,~

. ,]

, , j
~1

']

- <1', ;~

\jf ( _,'
1 N):
.

(2) dt,~. (1) ~J G>t (2:~ (2) ,~, (1)]} ~

- Lv(I)LUoJjj;Ui~'

~
. , , ~
.

i:

v' }.

U-

,;,} :,'.' " .: ;

.'

, u,.u -
\

hl'cr(l) + ~[! <I'~ (2~~).. (2) d1:2cr(1) - f '~ (2~:a(2 d1:2').. (1)] = cr''
- \jfj;
:

\jf (14.1):

h1 L <I'!L (I)Ufii ' +

+~

t, [f '1 (2~:.

!L

(2) dt,'i\< (1) -

U~jUVjU!Li -

L L
V

[~: (2~:, (2) dt,~. (l)]

vj == .

ji<l'v (I)U

(14.3:

j=1

""

"

LUvjUj).. == o)..v' (14.3) i

j

164

\jfj(2)\jfj(2)dV2
2 HeKOlfopoM

"

dV2' ,
I dq2,1'
{< 2, r ,
1, :dq2/'12'

- \jfj (2)\jf j (2)d1:2

r12

165

 , ~,
, I"',

, t \jIj (, \
~ , Q'

i\: \jI).

'i f

\jIj'(2)\jIj (2)d't2

1i2

~:
,lf ,
, .. ~~~
. 1 f;k,;Ii~~il;
}>

::n \IIJ' \11;,

Il; .~ ,~ 06u, t 7"" 6:-t.

,f \jIj (2)\jI; (2)d't2

( ,:)

*" 'i,

(
= 1),
' 1 \jI;

. ,

i,

, :.

JCJCUU. er '
, , '

1'

1i2

, ,
, "
' ( . ~).
, ""
.

, ''\jlj

\j!;

j(1)\jI j(l) = J\jI!~2)~; (2)d~2\j1 j(1),

,

( ~ <6]

QI

::: LKj(l).
j

J = I,fj(l)
j*;

J1 It
,

\jI;,

: '
\jIj (14.4) N,
(N-:l) ~. , Iil ,'
r , ,',
~.,.I<: , <;\. (

' , ~'
~'

, [2

(14.4)

.
, (14.4)
, . . , .

, ,
., < .
,
N ':l, ,;.
\j!; ,
j, P<l;BHOrO i.
,
, \j!;(1):

f \jIj(2)\jI;(2)d't2.
1i2

166

167

 . . .' ..;. . ... . . , . i. . . )

. , "

,' (N -

1)

\jfi(1)

(N - 1) ~;

.
I< 'Jfi(1)He ~.

( uu), Ii.,

j ri , i, , '
.~ \jfi(l) . ' N'1'.

. .1
~9' , :

iI

10 . .
~')i( , .)19 Q ,
: . . J1i~
","-

, 'k-7 : '1'0
, ' Q \jf ki( 1) :
\jfaC1).
'1'k -7 ' . -

, II/-,

('k-7jilj') = hak + .2:

J",k,a

([ak Ijj] -[aj I jk])

=;F~k'
.

, , , Fak .
, J(i:'

, .~: l15I' ' k . ~' ,

(' k-7a jill '1' ), . ;:

u. Teope~a ,
-,
~~ .l!tl J;I9,

9tlII~Q:i~: (. .. 15). '.;.' '.... , ,

:,

li =Ki,

.. j= i ~

, qj

\jfi( 1)' .

-, X~
- , . ~
, I1,i

' fI: :rey~() , ~ m~i: Xf\PT ~ ;;I. 'f . .,~.,J;i q~;q;

,;I" QQ:

"', ~tj:,'~Ji;:
: .:..- N h.'J!~(i=J;,~;.;.... ,.N),
N - ), -
\jfa ( = N + 1, N + 2, ... ). : \jft
.

:r () .

,\~

14.4..

'

~:

! F , ~.

, ~ : '

. IIY~. ~.I . . 6~ (! . e~ .yMepOB. .ft. .'.

l), , (

\jfki(l ( ;'
, , '.:;), , \jfa(1):

168

'~ :
J<.:[

.
.
.
,

\jf;= \jfi +b\jf, ..

\jfi:

r~ :

:, :
' . , ..

'1'0 (1, 2, .. " N) = qet['lfl\jf2 ... \jfk '" \jf N1,

O\jfi == \j!: (\jf; I \jfj} == (\jfi!\jf)+ .(\jf I \jf) =

'k-7(l, 2, , .. , N) = detl\jfl \jf2 ... \jfa ... \jfNI.

,:\ .
, : ,

169

 Jl
, :

. {'Jfi} :::

'?:. N) -

1, 2, .,.,

-,

(14.6).

, ' ;

'[; , '[
, {'I'i}'
Q {'I'a}, :
'[
. ,
,
, -

':

8' ::: det 10/1 ... 'Ii;

.~

... 0/N 1- det 1'1'1 ... '1';

... '1' N 1:::

::: det 1'1'1 ... ('1'i + .'1'~) ... '1'N 1- det 1'1'1 ... '1'i ... '1'N 1:::
::: '-.dtl'Jfi \.. 'l'a .... '!iNI ::: .' i -+
(14.5) F.!1
, d:il

(' i-+a

IJlI ') ::: ,

' i .... a -
'l'a 'l'i ,

'Jfi'

. ~.;

'.

. ., . . .. . . .'.
.'

(' ;.-7~

IJlI ') =

;-) .,

, .

'

u
,
~ .

14.5.
, 'l'a -

; J

, . , - ...
, (. .

'l'i, i::: 1, 2, ... , '

, F ~

'Jfi 'Jfj :::

... , N):
~

1,:

F'I'i ::: L,if'l'j.

j=l

'1'; ::: <Pi(X.

(14.4)
'l'i::: <;.

- r.. ~
, lI
-
<pj.
: - ,
:

d I'

-.. ~,
. -.

.. .~, :

' ::: L, [' [(1, 2, ... , N)::::L, [ detl'l'll 'l'2l ' .. 'l'NlI.
[

170

...

(14;1

.....

"

'"

F <Pi(l)::: h<pi(l) + L, (! j

.-

j )<pi(l) ::: i<Pi,

j=l

P~~(1) =h<p~(1)+ f(Jj -Kj)<p~(l)::: ~<p~.

(14.7)

j=l

171

 () ~(q),

~a

~~

-
, ,

14.1.
:

{/ -

- ; -

-++-++-++-

"

= q,

~a

~~

N/2

ERF = 2

.,"

~i +

L L
i=J

,(,,)

.('1. "~'

N/2N/2

(2Jij -Kij)'

j=1

."

, , <pr = <p~ ;
- .

Jij = [ii I jjj; Kij =lji].

14.6.

-

N/2

.'

: ,

- ('1' == <Pia \jf = <Pi~)'

+1/2
-1/2. ,
.
- (Restricted
Hartree- Fock - RHF).
- ('f'RHF)
:

<] (l)(l)

'f'RF(I,

1
2, ... , N)= Jiii.
N!

<! (2)(2)

<] (1)~(1)

<1 (2)~(2)

<]

<2 (l)a(l)

<2 (2)(2)

<P2(N)a(N)

<2 (l)~(I)

<2 (2)~(2)

<P2(N)~(N)

(N)P(N)

~~.;p',>j'.r .:w-f:~:c ?~\ '.;

/':._,

~!;\J.~?f'~i.;.

";i\

<PN /2 (N)a(N)
<PN /2 (N)~(N)

;":'"

Kj )<pi(l) = i<Pi(I).
'n;.....r',,~~-i~.f'/~,

;;:

.:f''

,
(

, ,

, ,

. . .
(. .

15)
N/2

i (. 14.1, ).

14.7. -

.-.

F <! (1) == h<pj (1) +

(14.7):
,.-..

L (Jj.......
j=l

<PN /2 ) <PN /2 (2)(2)

<PN /2 (1)~(1) <PN (2)(2)

172

<] (N)a(N)

',:.;':.

L (2Jj -

F<Pi(l) = h<pi(l) +

- Kj )<! (1) +

-~

Lq Jj <! (1) = j<pj,

j=1

p~ (P~ (1) h~~ (1) + (Jj - )<pr (1) + f J;' <p~ (1) E~<P~.
=:

j=l

=:

j=!


-,

/3

(F;j) =

(Fo;JJ.

o~ ].

<7 <9. ,
(
).
, u
- (Unrestricted Hartree-Fock UHF).

('PUHF)

> q):

14.1, ).

14.8.

~~

. , -

,
.

,
- , .

Is 22s l ,

'I' ROHF (1, 2, 3) = det \<plsa <Pls/3 <P2s a \.

7,

9 (.

~a

det '<) ... <pfa ... <p~a <p~/3 ... <P~-p/3 ... <p~/3I

= 2(IS\h\IS)+(2S\h\2S)+2[IS Islls Is]+2[ls Is12s 2s]-[ls 2s12s Is].

[(<) (l)(l) ... <p~(p)a(p)<p~(p + 1)/3 ( + 1) ... ~ ( + q)/3 ( + q)] =

/3.

'P uHF (I, 2, ... , N)

L[ , F

ipI <7 <Pr. ,

, ,

') , n
- q
.
N
+ q
2q + n. , q

= - Als,ls <ls 11s) - A2s,2s <2s 12s) -

-A1s,2s<2s 11s) -A2s,ls(ls 12s).

(14.8)

<1" O<p~" <2" <;.

, :

,-

-
, -

~a

~~

, , ,
. UHF ,
, ,

~2

S .

(Restricted Open-Shell Hartree- Fock - ROHF).

('PROHF ) .
+ 1/2, q
'11/2. ,

174

2q

{ F 2s<P2s

~lS<PIS

= tls,ls<Pls

+ t2s,ls<P2s

+ t2s,2s<P2s
~ Is<Pls
* = t1s,ls<P1s* + E2s,ls
' <*2.
= tl s,2s<P1s

(14.9)

{P

"" 2s<P2s
* = t2s,ls<Pls* + t2s,2s<P2s
*

Is 2s :
~

F"
~

1~

= h + J 1. + J 2. - 2. 2s,

2.

~
=-(h+2J1s -Kls).
2

(14.10)

 (14.8). t

et

,
. 'q
: ij = (ij)* , j = Is, 2s) ,

. (14.91

- , .~

,
.
(!)
-
:

! = 2LJihii + L{aij[ii I jj] + f I ji]},

i
ij

Is, 2s. Tpe~

, , ,lo
. (14.9) ,

E2s, Is
Els,

2.

f <P~s F\S<pls dv ,
= f <pfs F 2s<P2s dv .
=

(l4.11~

*.
.

E2s,ls = (El s, 2s)* , Ta~'

F 1s '2' - . -.
,

. /; i- ; aij,

i j.

! ==

(14.11):

2L/;hu + L

{2[ I jj] - [ij I ji]}.

ij

. ,

f <p;s(Fls - F2s)<Plsdv = .

. .

(14.10) 'l. '2'

. .

f <]' (Fls - F2s )<P1s dv = '2 (J12s, 1, + [2s Is 11s Is] + [2s ls 12s 2s]) = .

. .

! = 2 L h;i +

. .

L hmm + L {2[ I jj] - [ I ji]} +

ij

. .

. .

{2[iilmm]-[imlmi]}+-

L{[mm Inn]-[mn Inm]},

2 ,n

. ., . .

(i,j) (, n) .
,
n
.

. .

'f'1s-;2s(1, 2, 3)

= detj<plsa <P2sf3 <P2saj,

! = 2

. .

h;; + h",m + h nn +

{2[ 1 ] - [ij 1 ji]} +

ij

'PRoHF(l, 2, 3)

<Plsf3 <P2sf3 (
,
). ,

. .

+ L

. .

{2[ 1 ]- lmi]}+ L

{2[ii Inn]-[in Ini]}+

+[ 1 nn ] + [n 1n ]}.

* Yamaguchi ., Goddard J. , Osaura ., Schaejer . F. New Dimension to

Quantum Chemistry: Analytic Derivative Methods in initio Molecular Electronic
Structure Theory. - N. .: Oxford University Press, 1994.
176

177

 /;, , ~y, , .

- paCCMOT~

. ~
(.: , 1983) . (.: ,

Sz(I, 2, ... , N)=

= 8 Z(<P1 (l)(I)<2 (2)(2) ... <( )()<+1 (+ 1)~ (+ 1) .. <pN (N)~(N=

1976).

=.!.(p-q)(l, 2, ... , N)=s (I, 2, ... , N).

2

14.9.

~2

, (I, 2, ... N) (14.14)

Sz,

- !
-2
....
~

S Sz. :

M s

=1. ( - q).

(14.13) 2
'(I, 2, ... , N), (I, 2, ... N),

8z :
~2 ~ ~
~
~2 (N ~
S = S-S+ +Sz + Sz = .~>-i
1=1

(14.12)

J( LS+j
N J+ Sz
~
~
+Sz.
2

(14.12)

1=1

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

Sz

'

,s\ '(l , 2, ... , N) =Sz(I, 2, ... , N) = 8z (I, 2, ... , N) =

=s(l, 2, ... , N) = s'(l, 2, ... , N) .

82 (I, 2, ... N) (14.14), ,

+1/2 q - .
-1/2 ( + q = N).
-
: -

, -
~:

(I,

LS-iS+j. , i :::; ,
i

. i >

2, ... , N) = <1 (l)(I)<2(2)(2) ... < ()

()<+1 (

+ 1)~(p + 1) .. . <PN (N)~(N).

Sz.

(14.14)

Szi +1/2,
) = ( ), -1/2, ( = ~ (q ).

178

(l, 2, .. , N)

1
M s = -( - q).
2

S-iS+i i > q = N - ,
( ~,S-iS+j )(l, 2, ... , N) =

q(I,

2, ... , N).
179

[1

~2 (1, 2, ... , N)= 2(P-q)+(N -)+l (l, 2, ... , N)+

S

_(N + M s2) (1,

-"2

~2

"[ ~ +(

~ ~
N (-"2N)2] (1, 2, ... , N)+ ~S-iS+j(1,
2, ... , N).
[2+

, ,
(1, 2, ... N), ~ ,
-

, [~; -i S+

J. -

''''1
.

-
. RF(l, 2, ... , N) ( = q =
= N/2, M s = ):
RF(l, 2, ... , N)=<P!(l)a(l)<p2(2)a(2) ... <pp(p)a(p)<p!(p+l)~(P+l) ...

=As-is+j<p! )(1)<2 (2)(2) .. '< ( ) ()<l ( + 1)~ ( + 1) ...

+ i,

N/2

2, ... , N)

~ 'I'RF(I, 2, ... , N) - ~ 'I'RHF(I, 2, ... , N)"

2, ... , N).

~2

S ,

S=

, . . -

.
.

-
. 'P ROHF (1, 2, ... , N) > q, 2q
, n = (N - 2q)
, Ms = n/2

'PROHF(l, 2, ... , N) = RF(l, 2, ... , N) =

= [ <l (1)a(1)<P2 (2)(2) ... <j)q (q )a(q )<j)! (q + l)~(q + 1) ...
.(j)2q(2q)~(2q)<P2q+l (2q

i, j ::;; 2q

+ l)a(2q + 1)"'<P2q+n (N)~(N)].

S-iS+)

'P RHF .
q, 'P ROHF (1, 2, ... , N)

<Pi(P + O~(p + i)<PN /2(N)~(N).

j = + i

-q.

j >

.
,

> 2q,

~2

()<l ( + 1)13 ( + 1) ...

.. . <; ( + ( + i) .. <j)N /2 (N)~(N)] =

"[

= det/<Pla ... <Pi13 '" < <P113 ... <j)ia ... <213! =

180

j =

S_;S+} RF (I, 2, ... , N) =

'PRF(l,

= 'PRF(l,

'" (j)i(P + i)~ ( + i) ... (j)N /2 (N)~ (N).

!l ' RHF (1, 2, ... , N) =
= RF(l, 2, ... , N) :

= -dt!<l ... <Pia ... <ppa (j)1~ ... <Pi/3",<PN/2~! = -'P RHF (1,

~ ~

= A[(j)l (l)a(l) ... (j)i (i)13(i). < ()

i j

i > ),

2, ... , N) + ~>-iS+j(1, 2, ... , N) =

S_;S+(+i) RF (1, 2, ... , N)

'

''''1

j ::;;

+L's-iS+j(l, 2, ... , N) =
~

2, ... , N).

~ + (~ - q

= Ms(Ms

J]

S 'P RoHF (I, 2, ... , N) =

'I'RoHF(I, 2, ... , N) - q'l'RoHF(I, 2, ... , N)"

+ 1)'P RoHF (1, 2, ... , N)

~(~ + 1)'PRO~F(l, 2, ... , N),

181

.. - OTKP~~

n,

n/2.
ro - . 'UF'

(1, 2, ... , N)

> q,

. 'RF 'RF (14.15)

N/2 q , , , 52, ( 'UF)

'2n(n)
'2 + 1

( 'RF)'

. ,

'UF(l, 2, ... , N) = UF(1, 2, ... , N) = A[<pf(1)a(1) ...

... <p~(p)a(p)<p~(p + 1)~(p + 1) ... ~(p +q)~(p +q)] =

= det l<pfa ... <pja ... <p~a <p~~ ... <P~_p~ ... <p~~I
'UF S-i S+i ;l. .
, , i:S; ,
j> :

~2

S ,

. . -

.
- ,

, S.
, ,

,
. .

S-iS+i'UF(1, 2, ... , N) = AS-iS+i UF(1, 2, ... , N) =

= A[<pf (1)(1) ... <P~ ( )( )<p~ ( +

1)~(p + 1) ... <p~ ( + q )~(p + q)] =

~2

S ,

= [<? (1)(1) ... <! (i)~(i) ... <P~ ( )( )<p~ ( + 1)~(P + 1) ...

... <~_/( ... <p~ ( + q)P(p + q)] =

= det l<pfa ... <pjP ...

<p~a <p~p ... <P~_pa ... <p~pl =

= - det l<pfa ... <PJ-pa ...

<p~a <p~p ... <p~p ... <p~~I

-
. , UHF

~2

S .

,
,

S.

~2

S -Si(Si + 1)
Ps =
.
Si"S S(S + 1) - Si(Si + 1)
Si = Sl:

,
~2

S -Sl(Sl +1) I..s,'s. =

S(S + 1) - Sl (Sl + 1) S;
1

I..CSA(Si +l)'SI - I..CS;Sl(Sl +1)'s;

= .,.: S:!. .i_____--:-_-::S"-.i:-:::----:::-_ _ _ =

(<! I <p~) -

, -

182

S(S + 1) - Sl (Sl + 1)

=S's+

I..~i'Si
Si"S, Sj
183

 ,
Si = SI,

's.
, Cs'P s.

()

~2

S , S
~ ). ,
s tr
~2

S, n
.

+ -

= -f-j.

, ~,
.. . ,

,
,

~ .

(1933)

14.10.

-

.
. ,
. ,
, ,

. , ,
.

,
- +. ,
<Pi. ,

, <Pi,
_
.

,

. ,

,
- ~. ~

,

t:,

, .

. .
(.: , 1990).
, ,
,

,
,

+ = - {! \jf7(1)[-.!. ; - L ZA ] \jf;(l)d'tl +
+

f [f \jf7 (l)\jfi
j=1

(l)\jfj (2)\jf j (2) d't, d't2 _

'12

-f \jf7 (l)\jfji (l)\jfj (2)\jfi (2) d'tl d't

!j2

'1

]}

_ F;i = _ f-j.

0,1

1- 2

.
~

-14,83 ,
-12,6 . , 2,23 .
,
, - Fe(C sH s)2,
.
6,8, 7,2, 8,8, 9,3 .
, -

184

185

14.11

:,1

el u

-11,67

-9,02

11,1

8,8

el g

-11,89

-9,03

11,2

9,3

e2g

-14,42

-12,23

8,30

6,8

-16,03

-14,11

15,50

al g

-16,57

-14,18

10,10

7,2

.~

* .: u
1972. - . 27. - . 2281.

., Deuynck

J., Veillard

~ s= 0,3.
,

// Theor. Chim. Acta. -

d- ).
, . ., ,
, ,

(.

14.1).

!' e!g, 2
, e2g, al g - d- ( 90
65 % ).
,

e2g al g

d-, . . ,

,
, ,
. . .
(elu. el g)
,
-.
e2g, al g 5 - 7 .

186

1. .
2. J .
3. ?
?
4. .
5. .
+
6. ~ 2

2 E2g[aIge~g]

15

ti
'Vi.
(. . 14).
.

,
:

15.1.
- "
. ,

- .

, ,

.
.

,
- .
- ,

( , ,

) .
,
, ..

. 'Vj(2)\jfj(2)dV2

.
,
.

dq(2),

-
,

( --).

e'Vj (2)\jf j (2) d't2 = dq(2)

~2

, , .

'V/2),

~2

(1' 1,

Z1)'

2,

1,

.
, ,

15.2.
-

- .
.
: ()
, .
, ,

- ,
, m
.
.

-:- ,
( -

188

189

) (~
, ,
).

u {<()}, J
~(I)
~
F . ,
{<p(I)}. CTapQ~"
.
~

F

{<(2)}. epa~
l
.

j
, (

1)- OP~

<;

XI!:

<Pi (1)

L Cl!iXI! (1).

(15.1)

I!=I

.
(
),

,
, -

. (15.1)

, - ~

(, Mep~

() = - L'jiS <7(1)<Pj(l)d't!,

). , - ~
, \
, .
(Self-Consistent Field - S<I)F)~

i,j

, ~

, !

i=ll!,v
+LLLC:iCViC~jCtj

. ~

(,
; . . 19). ,
-

;<j J.!,V

~2

~2
N

- L L , jiC:iCVj SX~ (I)Xv(1)d't! .

i,j=ll!,v

. 14.2), ..
.

(},'!

[] X~ (1) (I)X~(2)X2)d't!d't2 _ SX~ (1)x1)x~(2)xy (2)d't1d't 2]_

hl ( uu; .

() = LLC:iCViS X~(I)hIXv(l)d'tl +

, , ;

jl,

, ,

V,

, 't 1 .

. (. . 13)

15.3.

() = LL:iVV +

XI!'

i=ll!,v

+L L L C:iCViC~jCtj([!lV I (J't] - [jl't I crv])i<jl!,v 0",<

190

191

 "
9. , ( ) '

FC =

()

--=LVi~V+
c~;

,!

(15.3)

+L L L CviC~jC<j ([/lV I ] - [/l't I crv]) -

L L jiVjS~v,

. (15.2)
Il ,
(15.3), (.

j=1 v

,
(14.2), j,
}, C<j, '

' .

. 2) 8-1/2.
FA

= S-I/2F8- 1/ 2

. ,

,
I

.
C~; , (/l = 1, 2,'
... , )

C~i'

~( "'" + ~?~([~V I m;J-[~",J)- :P'j'S'" ]", = .

15.4.

,
.

,!

, P~y - .
,
P~y = (P~)*, .. ,
x~, .
,

()

= R(),

<).

,
,

. ,
. , ,

, .

Ei'

L(F~v -iS~v)vi

(/l

= 1,

(
- ) .

192

(STO)

m 1930- .

. , :

2 )n+1/2
R (r) = ( <;
,.n-1 -".

8,

=1

FC =

2, ... , ).

(15.2)

~(2n)!

193

 , Ka~
, . -::
, ~
,
.
~

. - ;
'r ( ,

= (a~A

+ )/;

= (

+ )/; Zp = (aAZA + aBZB)/Y.

Is

exp(-] )exp(-l) = exp(-]- aBrl) =

);, -

(GTO)

1950- . . . . .;
. :

g(l, , n, )
N(a, 1,

1
n) = ( 1[3

= N(a, 1, , n)x'y z n e-a.r

)1/4

22(/++n)+/2'++n+/2

(15.4)

STO

, OHa~
, l1

,
, (' , ZA) 11
(, , ZB), ,
:

2) .

, .

).

(2/-1)!!(2m -1)!!(2n -1)!!

R}B) (

TepaoB' 4/8 (

1, , n - , KOTOPbI}i
.
(21 - 1)!1 135 ... (21 - 1).

1, , n.

<)
(15.4),
g(l, , n, ):
N

XJ.l = 'LCiJ.lg(l, m, n, ai)

(15.5)

i=1
, ,
. 1, , n
, , .

N
1 ( )
6-7 ( ).
,

. ,

.
(l + + n) (21 + 1)
,
:

s-op-

, - ..

(, , Zp)

194

= (a~ + )/; = ( + ),

s-, ( ) s- ( Is- 2S-0)

- ( 2-, 2- 2z-~) .. -

195

 - STO-3G. ~
, ~
. ~

N . N-K1G
,

, - .

N - l1 G

.
: 3-21G 6-31G.

n
,

::
1) 1

( )!!

, !

double-zeta (DZV) , triple-zeta (TZ'1

;
j'

. ,

, . .
, , ;

2)

; -~
, - d-, 1
- f-; o~
'!l

,
,

,
,

3)

, . . ~

<.

. d-

(DZP, TZP),

. , ~

s-. ,'!

; , 6-31G(2d, f, ) ,
6-31G d-,
(- -

l . ,

[631/31/1]

, s-, ",

, BTO~
- , -
. - : - ",
, - . ,

) N-K1G (6-31G*),

(6-31G**).

m ,

(corre1ation consistent -

),

d-.

cc-vDZ, cc-vZ, cc-vQZ. ,

cc-vDZ [881/31/1], cc-vZ 18811/311/11/1] .. ,

lI
. aug--vDZ
cc-vDZ
,
.

1+ 1+ 1+ 1.3 +

+ 13 + 15 = 14.
() ,.
.:.

, m .

, (
DZV VDZ), (TZV) .,.
. ~

, ,

Jl . , 6-31G*

. .,.;
N-K1G N-K11G. 1

, :1

.,

196

197

1s- "

3,425251 0,154329
0,623914 0,535328
0,168855 0,444635

1
2
3

), STO-3G 6-31G:
6-31G(1) 6-31G(2). STO-3G

-0,466582 . . ( 6,6 %,
-0,5 ..). 6-31G (
-0,498233 .., 0,35 %) 6-31G(1)
6-31G(2) 0,427431 0,665449 .
'leTe
(. . 15.1). STO-3G
) ,

lI

STO-3G

x(r)

x(r)

0,4
.., .

= , 276934 -3,425251 + , 267839 -,623914 + , 083474 ~,168855\,

2

1s

6-31G
(. 15.2).

, lS-0

6-31G (i
- 6-31G(1) 6-31G(2):

6-310(1)
1

18,731137

0,033495

2,825394

0,234727

0,640122

0,813757

I
6-310(2)
J 0,161278 I
;

6-31G 5,5 , STO-3G.

, ls-

r = . 1s-

1,000000,;

r:

d<p(r)

~ 1""0= -2Z<p(0).

15.1

:1'

ls- ( 1s
q

(15.6) ,

r =
. ,
(15.6),
, lS-0,
.

0,6
0,6
0,5

0,4
0,27

0,4

_ _~

2
.

15.1.

, ..

,'
1

1 - 1s- ; 2 - STO-3
, 4 - -31G: 6-31(1) -31G(2) ('.
1s STO-3G )'

198

0,3

. 15.2. 1s (1) ,

6-310 (2)

199

, 6-IG (!

, .

lS-0)
r < 0,005 . .:
I

( ), .

.~

5484,671660

0,001831

52,964500

0,232714~

825,234946

0,013950

16,897570

0,470193

188,046958

0,068445

5,799635

u ,

0,358521

, . . .

,
,
.

, ~
, , ~

u ,

-, .

.
,
.

, ~;

: STO jJ. ~ = 1,~

GTO:
~(l, r) =

,
( - )
.

I. CjJ.kg(PkjJ.r),
k=!

STO

jJ. ~ ~

.
(..
):

~(~, r) = I.CjJ.kg(<XkjJ.r),

V(r) = VL(r) +

k=!

CjJ.k ; <Xk = ~2P!k"

1-

L-!

/=0

=-/

I. I.

ml)[V,(r) - VL(r)](tm 1,

L -

(15.7)

r ~p
. .
,

1 . V,(r)
1 ,
:

Pk

,~

15.5.

[.

(15.7) Ilm><Zm

v, (r) = I. C/prnlp-2e-Z/pr2 .

. ,
, ~

, ,
/ , nlp

. , . ~-:
,
, ,

200

z,p.

. , -

201

( ,
)
.
, '.

5
4

, '

,
.

.~

, ,

.
.

(Effective Potential - ). '

, ..

R
3

,
, .
,

('
) .

1) 4d- 5s- ,
36 ( ,

-1

);

) ( ).;

0,4

. '
3-21G (a.e.~,

-17,87, 3d -11,65, 4s -3,47,

-2,23, 4d -0,58.

-0,4

4s- 4-, , 4d-

,

4d-

-0,8

3d-.

"
. 15.3 3d-,j

-1,2

4- 4d- , -'!
. 3d- , 4d-op-j

0,15 0,5 .. 3d- j

r= 0,32 .., 4 ...... 1
1,02 .., 4d - 1,2 a . e . J
, ( ;'"

( ).

202

4s-

4- Ka~

\'

r = 0,5 . . 4 .1

, ..

2) 4s- 4-, ,
; (28

, ..

15.3.

3d (), 4
(

(6), 4d ()
3-21G)

15.4

~M 4d-op5 . , -

203

v,

R
0,6

. .

100

0,5
0,4

50

0,3
0,2

.,

0,1

15.4.

, ..

4d- (

15.5.

5 R,

HW (1)

..

SBK (2)

d-

SBK)

, ~
.

'

, . . . . *
.. , . , . ..**.:
HW1
SBK . HW
- , -'

SBK -

GAUSSIAN HW Lan12,
Lan12MB ( )
Lan12DZ ( ).
HW SBK d-
. 15.5.
-'
, .

15.6.

*1

(.

'
,
,
, .

s- - ,
:

s-

d-

f-.

, , , -

* . J., Wadt W. R.// J. Chem. Phys. - 1985. - . 82. - . 270, 284,

** Stevens W. J., Krauss , Bascll ., Jasien . J.// . J.Chem. - 1992. .612.

204

299.
. 70.-

15.1

15.6)

Ti-Cl(l)

0,2218

0,2213

Ti-Cl(3)

0,2317

0,2318

Ti-C1(4)

0,2317

0,2267

Ti-O(I)

0,2158

0,2162

C(l)-O(l)

0,1211

0,1213

*1

HW;

3-21G*.

205

15.2;

*1
(.

1(1)- Ti-Cl(2)

101,6

100,0

,~ Cl(3)-i-C1(4)

159,5

161,1

74,1

76,1

,:

HW; ,;

3-21*."

15.3'

*1 m
()6 ( = , ,

W),

-'2

2'3

ccSD(T)'3

()6

78,2

233,0

180,7

1548'4

()6

100,4

183,3

159,8

169,58

W(CO)6

136,0

220,5

191,2

192,58

'1

'

HW; -i

'

6-31*.

'2

- . ,1

*]

2 (. .

17).,

'4 , -, .

, (, ), -'

, , -i,
.
, -:
. -i
.

*, ;

,

* Frenking G., Antes 1., hm . et /. // Rev. Comput. Chem. - 1996. -

206

*1

15.1-15.3).

15.6)

O(1)-Ti-0(2)

(.

8. -

63.

1. 6-31G.
2.
6-31G 6-31G*?
3.
2?
4. ?
5. ?
?

16

. AAJI

1I
II .
, ,
110 ,
.

1- 2-

16.1.

I Xl) = N fJ*(l',

)(;

()
1950- . . - .-.

y2)(xlx2I x )x2) =

. .-.

*.

N-
"(l, 2, ... , . -

2, ... , N)J(l, 2, ... , N)dx 2 dx '" dx N,

N(~-1) fJ*(l',

2', 3, ... ,

N)J(l,

(16.2)
2, ... ,

N)dx ... dxN .

2-
:

I X~ ; ) = 2)*(; X~ I )2)'
2) (; ; I ) 2) = -) (; ; I ) 2)'
2)()2

fP) (X{X~ ... X~ I 12 ... )

:

)({2 ... ; I 12 ) =

(~ )! * (1', 2', ... , ', ( + 1),

0'0'

N)'f/(I, 2,

'00'

, ... , N)

dxp +)dxp +2 '. dx N .

,
. ()

(16.1)

J(l, 2, ... , N) ,
.

( ).
, (16.1) ,
. (

r(Xj) = () )
()2) =
= r(XjX2 XjX2)' ,

1)-

)dv)

')

dv)

0"),

.
( ) .
2- ,
, r(X1X2)dv)dv2,
: ,

dVl

- (. .

') 0"1, u
dV2 '2

):

0"2,

. , -

(16.2):

'

f r(xl)dx) = N, f r(X1X2)dx1X2 = N(N2 -1)

* Lowdin .-. / / J. Chem. Phys. - 1955. -

208

. 97. - 1474, 1490.

(,

N(N - 1)/2 -

). 2-

209

 ! 2 (! = 2)
(16.2).
, 2-
.
, ,

f'P*

(~ I,'Qij ]'Pd't = N(N -1) 5'P*QI2'Pd't =

2!

N(~ -1) f['P*(1', 2', 3, ... , N)QI2'P(I, 2, 3, ... , N)]x; =Xl, 2 =2

dx!dx2 (dx ... dx N ) =

(16.1)
(transition matrix),
jJ:

I, (il XJ)

= Nf'Pf(I',

2,

.. ,

N)' (1', 2, ... , N)dx 2 dx ... dx N ,

I, ({2 I !2)
=

N(~ -1) f'PHl',

2', 3, ... ,

= f[Q!2y(xi x 21 XI X2)x;=Xl,X2=X2]dx1dx 2

.
3, 4,
.. , N, , ,

N)' (1,

2, ... ,

l- 2- .

N)dx ... dxN .

. Q

m .

Q = f'P*Q'Pd't =

~~

Q = Qo

+ I,Q; +, I,'Qij +, I,'Qijk + 0.0,

I

2.

ij

3.

ij

(16.3)

+ 5Q1Y(xil xl)dx1 + fQ12y(xix21 xJ x 2)dx1dx2 +

+ f Q123(i' I I2 )dx1 dx2dx + .. 0

ijk

(16.4)

-, - ,

, , ..

( , )
.
, ,

paBH~ .

Q _

, .

l-
2- ,

5'Pi ' d't = 5 ! YI, (' I !) dxl + 5QI2YI, ({ 2 I I 2 )dx! dX2 + ...
,
' ! '

'* '

5'f11'd't = 511YI, (I I xI)dx l

.

, ,

.-. ,

210

N(N -1)/2

2!

I,'Qij
ij

.
, .

211

 , -, '
, .

' ' L -

.,

-
11

't'kp 11
't'k2

, ,

11
't'k

\jf/p \jf/2' ... , \jfIN .

ki ~

. -

!(ki 1 Ij
(

).

IlblX

\jf /1 \jf 12 \jf IN

IIN ) = det

(-l)q p;S(k, 1 1,)s(k2 1/2)" .s(kN

d't =

s(k 1/) 1=D KL .

, , ' = ' L,

:
, , DL = 1.

det 1 s(k 1/)

' 'L (
)

, D~L = .

~ , -

{\jf,\jf2'" \jfM}

+ "I hijYji + "I "I [ij I kl] rt/

i,j

rt/.

(16.4).

(13.2)

Il 2-

= 1):

1'' ' Ld't =1\jf~1 (1)\jf~2 (2) ... \jf~N (N) det
=

ij kl

(16.5) ,
.
1- , ,
.

, . .-.
, ,
,
, . . .

( -

; . .

14)

2-

1-

(16.5)

(ll 2)\.
(2 1 2)

. 1-

(,1

(k) (/)

Xl)

I, \jf~(Xl)\jf/(Xl)I,I,C;DL(k I/)CL!I,I 12 =

k, I

k- I- ;

Yik -

1- -.
v
,

Ykk

212

I,Ykk

16.2. ,

k,l

1/) -

1- . ,
- , ,

= I,\jf~(X,)\jf/(X,)Ylk'
DL (k

, 2-

= N.

, 'l' ,

().
, ,
, () .

. ,

213

C:iCfLi

: 1) Qj
; 2) . ~
, ':'
,

V"'fL

),

. -.:
.
..

qfL ::

,
:

fL

(16.6),

LLC:iCViSfLV
fL V

LC:iCfLi
fL

LL
fL V"'fL

C:iCviSfLV :: LC:iCfLi
fL

2L

(, '

(C:iCfLi

).

n.
,
. ,

.

1955

WfL

PfLVSfLV'

WfL

.
:

. !,

e :

) :
, ~
.

- . 1968 .

+ L C:;CV;SfLV ):: PfLfL + L

1 ~ 2 , 2 , 2 - , 3 -
. , , (

C:iCviSfLv'

fL<V

, XfL

2 f.."

XfL:

()
(Q) Z -
. (), , .

fI<; ,2 dv = L L C:iCVi f X~Xvdv = L L C:iCViSfLV = 1.

fL

+ L C:iCviSfLV'

. . :

* .
,

(16.7)


, ~ ~,

( ) .

, ,

. (V) ~~ ,

CYM~e KpaTHOCTe~ (W),

(. . . . , . .

. . **):

,
XfL

* k R.S. // J. Chem. Phys. 1955. - V. 29. 214

<Pi,

1833, 1841,2338,2343.

* .., .. // . . -. - 1973. - Ng 16.119; 1976. - NQ 16. - . 98.

** Arstrong D. R., Perkins . G., Stewart J.J. . / / J. Chem. Soc. Da1ton Trans. 1973. - . 838.

215

VA

=L

;<

W .

,
.

, ..,

. ,

.
,

CTBO~ . :

-
NAO ,

L L (PS)/lv(PS)V/I'

/leAveB

~ '

, ~

, .
xoo~ ~ (Natral

Atomlc OrbItals - NAO)*.

. 16.1,
, .

, ,
.
,

.
,

( (16.7.
,
,

(Natural Bond Orbitals - NBO).

NAO,
, NAO
1,8. NAO

,
.

,
,
.
NAO,
.

.

(. . ) .
:

.
;

.

;

~.

,
.
~ ,

, ,

.
, ? -

* Reed .., Weinstock R.B., Weinholder F. // J. rn. Phys. - 1985. _ . 83. _ . 735.

cr

+ C~

1;

, -

+ ,

.
cr
(cr, , 8),
.
.
.

( ) :

cr~B =

'

, (
), .

216
217

NBO ...:
- . NBO

.

:

(cr * jFjcr)2

* = -2 -'---*---'-

*,

6 :

() ,

()

- .

99 %.
*
(. 16.1, 16.2).

(.

. 18). (
) ,

.
_
.

. .
.

3, (.
19).
lt- 2-,

1/.J2,
. cr-
. cr(2s) cr*(2s) 2-

, cr(2p) 2s-, -

.: Bridgean A.J., Cavigliasse G., Jreland L. R., Rothory J.// J. Chem. Soc.
Dlt s. - 2001. - . 2095.

218

3L

3L

(cc-vDZ)

(tzvp)

(cc-vDZ)

1,00

1,00

1,00

1,00

1,00

2,66

2,64

2,62

2,38

2,52

2,27

2,25

2,25

2,09

2,25

N2

N N

2,87

2,84

2,87

2,89

2,93

N 10

N-N

2,31

2,27

2,32

2,34

2,38

1,75

1,71

1,70

1,63

1,83

F F

0,99

0,99

0,98

0,94

0,97

HF

1,05

1,06

1,05

0,91

1,04

1,03

1,04

1,03

0,93

1,04

0,97

0,97

0,98

0,93

0,92

3,15

3,11

3,12

3,06

3,12

HCN

16.2

() ,

()

3L

(cc-vDZ)

86
(cc-vDZ)

(cc-vDZ)

(tzvp)

(cc-vZ)

LDA

0,99

1,00

1,00

0,97

0,97

CF4

1,27

1,24

1,22

1,17

1,23

1 4

1,06

1,04

1,04

1,09

1,06

CzH2

1,04

1,05

1,05

0,97

0,93

2,71

2,68

2,70

2,85

2,82

0,91

0,91

0,92

0,90

0,97

2,23

2,21

2,20

2,09

2,12

0,97

0,97

0,98

0,97

0,97

1,12

1,11

1,10

0,97

0,95

0,93

0,94

0,95

0,98

0,97

1,46

1,45

1,45

1,39

1,38

CzH6

86
(cc-vDZ)

F2

LDA
(cc-vDZ)

16.1

6 6

219

 16.3

162

()

.~

2 6

CF4

LDA

86

(cc-vDZ)

(cc-vDZ)

(cc-vDZ)

(tzvp)

(cc-vZ)

0,97

0,97

0,97

0,96

0,95

1,11

1,09

1,07

0,96

1,01

1,00

1,01

1,01

0,92

1,02

Cor(1s)

2,00000

0,94

0,94

0,95

0,95

0,95

Val(2s)

1,04095

1,05

1,08

1,07

0,97

0,98

Ryd(4s)

C-N

3,24

3,18

3,20

3,05

3,26

Ryd(3s)

-,

0,97

0,98

0,99

0,98

Val(2p)

0,79968

0,97

Ryd(3p)

0,46

0,47

0,47

0,47

0,48

0,75

0,70

0,67

0,60

0,54

0,98

0,98

0,98

0,99

0,98

B-N

0,80

0,77

0,75

0,57

0,62

N-H

0,97

0,98

0,98

0,90

0,83

0,83

0,83

0,85

"uu. ,

() ; -

*1

STO-3G

6-31G*

aug--vDZ

1,99998

1,99997

1,99987

0,79063

0,73070

0,71237

0,00469

0,00460

0,00000

0,00000

0,59583

0,59575

0,64636

0,01908

0,01270

0,02665

0,00006

3-2

Ryd(4p)

0,00527
-

Cor(ls)

2,00000

1,99983

1,99993

1,99992

Val(2s)

1,91622

1,85803

1,85778

1,86088

0,97

Ryd(3s)

0,00037

0,00064

0,00016

0,87

Ryd(4s)

0,00030

0,00004

Val(2p)

Ryd(3p)

1/,

+1

--1. do-

~ . 2s- 2-
,

, 1/,
2,863.
,

.

4 (. 16.3, 16.4).
,
0,135 .

. 16.3 16.4,
OCTO~HX NAO 1s .
,

. ~
, -

Ryd(4p)

1,74126

1,81233

1,82777

1,82744

0,00034

0,00019

0,00065

0,00004

'1 : Cor - ; Val - ; Ryd .

, ,
.
6-31G*
aug--vDZ ,

.
0,3 %.

,
(

):

2-,

1
- 2s 2p2,5.

221
220

Val(2s,

STO-3G

2)

0,9695

3,44

3-21G

0,9373

2,730

6-31G*

0,8989

aug-cc-pvdz

0,8830

.~

Ryd(s,

Val(2s)

Ryd(s)

16.4

110

NAO*

C-F

CF

NAO

7,14

+0,56

-0,14

+0,41

-0,10

SI,04p 2,40

Sl,92p 5,22

0,085

7,295

0,014

+1,18

-0,30

+1,08

-0,27

sD,79i , 94 3sD,01

Sl,86p 5,44

2,519

0,008

7,341

0,009

+1,40

-0,35

+0,98

-0,24

sD,73p l, 79 d 0,02

Sl,86p5,48d 0,01

2,500

0,055

7,343

0,018

+1,45

-0,36

+1,46

-0,36

sD,71i,793po,04

Sl ,86 5,48 d 0,02

. 16.3.

Ii

~. f)
1S-0 , paBti

.

.

. ~1

v-F 1,99254 , 4

26,85 %,
73,15 %. NBO
= , 5182

_+
(

+ , 8553XF,

XF :

= , 5000(2s) + , 0025(3s)

+ , 4980(2 + 2 + 2pz) +

XF = , 5106(2s) + 0,0178(3s) -- , 4957(2 + 2 + 2pz) +

-- , 0008(3 + 3 + 3pz) + , 0243(dxy + dxz + dyz ).

,

1,98736

(!PF),

!PF = , 8597(2s) -- , 0097(3s) + , 2948(2 + 2 + 2pz) +

+0, 00 17(3 +3 +3Pz)--0,0064(dxy +dxz +dyz ),

- F.

1,93510

*- - (

0,12659) 3-15,5 /
222

................................... 41,40010 (98,5717 %)

................ 0,50637 (1,2056 %)
......... 0,09352 (0,2227 %)

+0,0302(3 +3 +3Pz)+0,0330(dxy +dxz +dyz ),

................................................................................ 42

, s3_
. ,
-
.

[Fe(CN)6]4-.

B3LYP Lan12DZ,
3s 3.
. 16.5.
( )
.
-

4s,

3dx2 _ y2

F()

t2g
-

223

 . , 1

(. 16.6). C-N

n- 3d(Fe)
"--7n*(N-). . 16.5

NAO 4s.
- Fe(II)-(N-) xo~

. , 3d,,- 1

n*-

CN-. . 16.6 ,
NAO ,

).

16.5

[Fe(CN)6]4-

1.
3
: 11S, 21S, 2 S,

1; Is2s.
2.
- .
3. 0,96[ <l <Pl~[- 0,28[<2 <P2~[

NAO

N*

NAO

N*

Cor(3s)

1,98681

Pz

Ryd(5p)

0,00335

Val(4s)

0,44483

dxy

Val(3d)

1,90860

Ryd(5s)

0,03222

dxy

Ryd(4d)

0,00253

(3)

1,99787

dxz

Val(3d)

1,90860

Ryd(4p)

0,02653

dxz

Ryd(4d)

0,00253

Ryd(5p)

0,00335

dyz

Val(3d)

1,90860

(3)

1,99787

Ryd(4d)

0,00253

(/) .

Ryd(4p)

0,02653

dyz
dX2 _ y2

Val(3d)

0,95426

Ryd(5p)

0,00335

dx2 _

Ryd (4 d)

0,01242

Pz

(3)

1,99787

dZ2

Val(3d)

0,95426

pz

Ryd(4p)

0,02653

dZ2

Ryd(4d)

0,01242

5. NBO 0,7071 +
+ 0,7071piC2). NBO?
6. NBO -

NBA

16.6

[Fe(CN)6]4

q(Fe)

-0,214

-0,881

q(C)

-0,031 (-0,240)

0,142 (-0,606)

q(N)

-0,489 (-0,760)

-0,773 (-0,394)

W(Fe-)

0,498

W(C-N)

2,744 (2,838)

uu.

224

2,22 ..;

0,146 ..

( )

(W)

4. 3, -

<l <2

16.3.

(1[I).
,

CN-.
8

I\

17

() =

V'(r) - V(r)

II

, .
.

17.1.

17.1,

.
F(r) ,

, . ~

,
.

2 ,

- , TOMY;j
, Bpe'~

"

. , (-

, J

. - (
) .

BpeW!

. , 2

(. . 16):.:

= IhijYij + II[ii I kIJr~/.

i,j

i,j k,1

, -
, . .

155 /, . . .
(. 17.2) , 2
(-198,668764 ..) 160 / ,
(-198,729914 ..). ,

v,

F,

300

,
(),
,

1
2
200

. , V(r) ,
ls- ,

100

V(r) = (1s(r'2dv' /Ir' - rl

' , ls-

0,2 .

Z. ,

z r

-0,15 -0,10 -0,05

226

=1/Ir -

r'l.

0,05

0,10

0,15

. 17.1. V () = (ls(r'2 dv'/Ir' - rl (1)

F(r) ==

V'(r)

1/1 - ' 1(2)

227

, ..

__-----1

-198,4

17.1

-198,6

-54,6122

, . .

-198,8

Do,

9,760

(" -

-199,0

,
\

1,0
.

17.2.

1,5

2,0

2,5
3,0
R(F-F),

3,5

4,0

4,5

E(N 2) 2E(N) + Do + (0./2, . .

, ,

- (1),
(3)

(2)

EN/, . .

(2E N), . .

Ellonr./(N2)

= E(N 2)

, . .

, ,

2 : -::

, .

.
,

98 %

130 / (
) 154 / (
);
. . 17.2 ,

(0,145

).

(Eeor)

, -,
:

Eeor =
228

- F (N 2 )

= Enonre/(N2)

- EHF (N 2),

-0,02732
-0,05464
-109,5338

N-N

-108,9956
-0,5382*

..

-109,5884

2EN', . .

17.2 , :r(
: -) = 4,7 .
-198,326917 .. - , ,
.

Ecorr(N2)

2358,07

-0,1660 .. =
- -4,517

*
-0,3722

:
..

(
,
).
,

. 17.1*.
.-.:
,

,

-
.

,

.. -

1987. - . 59.

.: .

'

..

229

 - , -'
, , ,
,

, .

J'

14.2.

, -
*:

. ..;

R ....................................... Re

-;

" . ...................... -0'148028

(. . 16) ..: .
. , ...,

, -;:
. , I
, 1j
. ~:

~.i
- . - -{

.
":

(. ). ~
. l
<4
- , , KO-i
.

. CKa~

-;

: - , -.

(,

).
,

(
).
(
) .

,
.
,
.

2Re

-0,310067

, ..
, ,
,

,
2 .

20.

.
,

,
:

,

- +.

.
.

- ( ,
) :
. ,
.

, - (

-) -
. ,
,

. -
, -,75 . .
: -1 . .
,
7 - , ,

. ,

230

1,5Re

-0,210992

17.2.

,
- {'I'i}' N-

* Ha"ison R.J., Handy N.G. // Chem. Phys. Lett. -

1983. - . 95. - . 386.

 'i

'.

l Q (I,

2, ... , N) =

I,Q(l,

2, ... , N),

(17.1)

(17.2~

- ~.
- - {'I'iH

, -

(1,2, ... , N). ~

,
~

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

u . (17.1) ,
- (
),
, ":
, .

(17.1)

CKQ , ,
-, ;
:..:
. , ~
,
- .
, ( ) -.
. (17.1)
,

{'I'i}:

. ,

()

(
),
(). ,
,

(Configuration Interaction - CI).

.
.
,
(reference). m

= ~N!
;;-; 1'1'1'1'2 ... 'l'NI

{'I'J
-. ,
, i,j, ... (i,j= 1, 2, ... , N),
() - , , ... (, = N + 1, ... , 2,
- ).
,
,
- 'l'i, 'l'j, ...

- 'l'a, 'l'b, ...

'l'i, 'l'j, ...
'l'a, 'l'b, ... ,
- . -

7,

ijk

- f/, -

..

.
- S, -, -
- D, , Q ..
:

(OIHIO)
(SIHIO)
(DIHIO)
(TIHIO)

(OIHIS)
(SIHIS)
(DIHIS)
(TIHIS)

(OIHID)
(SIHID)
(DIHID)
(TIHID)

(OIHIT)
(SIHIT)
(DIHIT)
(TIHIT)

(OIHIQ)
(SIHIQ)
(DIHIQ)
(TIHIQ)

(17.3)

, -
:
,

, .
, -

(17.3)

(OIHID)

(SIHIS) (SIHID) (SIHIT)

(D/HIO) (DIHIS) (DIHID) (DIHIT) (DIHIQ)

(TIHIS) (TIHID) (TIHIT) (TIHIQ)

(OIHIO)

232

233

 , , -'
, '
.

CIS),

.,

. !
-

(SIHIS) .

.

.

(0IH10)

.
, ,
N 2 -.
!

, , .

CIS

. ~

= 1 -

(17.1)

.,

(SIHIS)

. ,
, -

(2)!

CIS.

CI, ,
, .

, CID (Configuration Interaction, Doubles);
,

CISD (Configuration Interaction, Singles and Doubles);

CISDTQ ,
. ,

CISD

N!(2M -N)!'
. . .

. ( ) (,
(CISD) (CISDTQ.

.

17.2.
CISD

NM

NNMM

' CISD = + I, I, i7 + I, I, I,
i

f! -

; -

<j

m * ,

L ij 7/ .

<

CISDT

CISDTQ

94,91

99,97

94,70

95,47

99,82

94,44

95,43

99,84

HF

95,41

96,49

99,86

I!.

Ij

(S IHI ) .

( Configuration Interaction -- FCI),

CISD

CI

17.2

234

95 %

.
-

100 % , FCI.
Harrison R.J., Handy N. . // Chem. Phys. Lett. - 1983. - . 95. - . 386.

235

 17;~

, ,

CI ",1

, . 12,

CISD

568

2
--1

361

CISDT

CISDTQ

28698

3203

17698

FCI

132686
256413

4029

19925

137321

HF

552

6712

48963

944348

* .: Harrisan R.J., Handy N. .;; Chem. Phys. Lett. - 1983. - . 95. - .:

386.

.
(
), (
).
CI.
, ,

, -'
. ,
, (

) - (Configuration State Function - CSF). ,

CI.

(
- C2v ) -246,483752 . .
GAESS.

<P19(al)
<22(2 )' ,

0,66854(1 <22 <P19~ 1+ 1<P19 a <P22~ 1) =

= 0,66854(1 <P19 a <P22~ 1-1 <P19~ <22 1) =
= 66854 Ji(1 <P19 a <P22~ 1-1 <P19~ <22 1 =

Ji

= 0,97257 (1 <P19 a <P22~ 1.121 <P19~ <22 1J= , 97257 sim'

236

Ji

461

1<P19 a <P22~ 1-1 <P19~ <22 I

'

17.3),

_
sim -

(.

"

: l 2
2
, ( )
- 12
I
, -

.
.i
- .

17.3.

,
.

(MultiConfiguration Self-Consistent Field - MCSCF)

, ,

I
. ,
:

1)

2)

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

. :
, ~ -

237

 . (

<l'*'

) ,
.

.
.

CI,

MCSCF,

. 8.
<l'*; Sl

f (;' d't

= f ( cos 8 + 7~ sin 8)( cos 8 + ;~ sin 8)d't =

= cos 2 8f d't+ sin 2 8f 7~;~d't+

, , ,

- .

- ,
.
,

= <l'* cos 8 -

+cos 8sin 8 i~d't + f 7~d't

J.

<1'; = <1'; cos 8 + <l' si 8.

f i;' d't

, 8 - .
,

+cos8sin8[J (;;~d't+ J 7~d'tJ = 1.

<l':

<I'~ = <l'

cos 8 - <1'; sin 8.

(COS8 -si8J
cos 8

, ,

( <I';<I'a ) = (<I';<I'a) sin 8

= f ((; cos 8 + 7~ sin 8)( cos 8 + ;~ sin 8d't =

=cos 2 8f (;d't+ sin 2 8J 7~;~d't+

, i~
.

<l'U,

.
,

U-

= J 'd't+ J d't =sin8[J ;~d't+ J 7~d'tJ =

<1" =

x[J i~d't + Jr~d'tJ,

- () .
( , )

U+ = (COS8 Sin8).
-sin 8 cos 8

<l'!

<1';

= <1'; cos 8 + <l' sin 8,

~* <I'~* -

238

(17.4)

(17.4). -
- , (17.4)
:

. -

239

,
.

~
, MCSCF
. (17.4)
,

G-

- , . MCSCF

Xpq ( ).

(17.5),

BeHc:r;Ba

-1
=X-GH
.

J~i~d't, J7~d't,

, - .

. ,
, ,

, .

.
,
.
- ,

.

MCSCF,
(Comp1ete Active Space
Se1f Consistent Fie1d - CASSCF).
:

;
( i,j);
,
( , ).
, q.
- ,
.
2, -

1)
2)
3)

:
2

= _ () / () .

(17.5)

.
, ,

(17.5) ,

, .

(17.5),

. ,
- , - ()
n
(n - 1).

240

.
,
,

. ,

(Comp1ete CI). ,

.
,

CASSCF

,
.

241

 - . , -. J
, ; j
, (" ,1
) , . j\

, .,.!

>- 1 >::: (1 +1' +1-1'2

+l
+ ...) I },
2!
3!

'1'

. , .l:1

::: 1'1 + 1'2 + + ... ,

, , '1
, , .1

, . , :

, B~

, . .!
I

CASSCF.

. .

10-12

H~

, ,

CASSCF ,:
,
,
. -.

.

(. )
:- (Multirefe-

rence Configuration Interaction - MRCI).

17.4.

,",

1";

~
ta tab

, i. i,

. CI, ~

, . ,
::: 1'1 + 1'2,
(Single) (Double) <S:CSD).

aHT CCD .. ~ CI,

,
, -

. , ::: 1'1 + 1"2

=[1+1'1 +1'2 +~(TITl +21'/[2

=1

+;2)+ ...] I ) =

> + I,tf 1f) + L L tf}b I f/> + ~ ~ "~:JiatJ 1f/> +

i,a

i>j a>j

i - :

:
:::

Ltf + L L ijf/ + ...

i,a

l,a j,b

(17.8)

(17.6)

(l + 2 + .. )

ij , ...

~
~
1 ~ T~)2
) 1 >
l'I')=I>=(1+l+2+'2(l+ 2 + ...
0=

(Coupled Clusters - )
I ,

. I

Ci,

::: Ltt ti ,

-, ~

. ,

(17.7)

i>ja>b

,
, .

ypa ~ CCSD ~,

() , -

243

':)

1 >

+ 1 ) 1 ) :::: 1 ) 1 )

( ).

Ci t i : , = -0,016409;
=-0,064232; t, =-0,011603; t2 =-0,064367. ,
Ci
(i' , -2,875263 . .
2

=1 ':) I ':),
(

,
.

CI :
~

':! = (l+ +)

( - ) I ':) = .

- .

(17.7), (17.8) ,

f ( - )':eed't ( lil - \ ': ) = .

CI .

. CISD CCSD

': eeSD = [1 + i\ + 7'2 + ~ (7',)2 JIcrg(X crgPl =

= Icrg(X crg~1 +
+t,lcrg(X ay~1 + t,lcru(X ay~' +

ay~1 + ~ t? '( au~' + ~ t? 'u( ay~1 =

;; Icrg(X ay~1 + '( crg~1
2
= Icrg(X crg~ I+ ",2t,
.J2
+ 2 + t, )lcru(X cru~l,
+t2 Icru(X

( m ).
,

, :::: .J2t,; 2

:::: t2

( lil - \': ) = ( \ -\(1+7"

=

+(

+ 7'2 + ...) )::::

( I\ ) +( I\7" ) +( I\7'2 ) +
\il\7' ) + ... - ( I > - ( I 7', > - ... =

=E HF + L L
i>j

>

t{j( I 't/> - = .

(17.9)

,
,
,

-, ;
, .

,

EHF + L L t{j( 1 ,!/> = E HF + ~ L t{jb(ab I ) = = E HF + E cor

+ t?,

+ (
STO-6G,

244

I ':> m
,
- :

i>j >

'>} >

Ecor = LLt{jb(ab I ).
i>j

>

245

 (17.9) ( 1 (f 1, (f} 1, ... , j

:

N - ,
-

(f /- /' ) = ,

(f/ / - / ') = ,

~ )(

t'JJ, ... )

...

". MeTO~

CCSD,

(Triple) , ':
( CCSD(T.
, , ,
'

(, <Pi, <)


**.
'

hj,

17.5.

-
. -
(n, n - ,
).
,
.
,

('P

-
HF).

..........

()

, ,

87. -

**

Head- Gordon .,

Raghavachai .

/ / J.

h.

Phys. - 1987. -

5968.

Crawford . D., Schaefer . F. / / Reviews in utatinl histry. V.14 / eds . . Lipkowitz, . . Boyd.N. .: Wiley and Sons, 2000.

246

=l-E.i'
I

,
- :

() + E(l) =('P HF /HO\'P HF ) + ('P HF \W/'P HF ) =

~(~HFI~Fil~HF H~HFIH -~Fil~HF) ~

=('P HF /H/'P HF )

== E HF

\(

' HF \W\ qt

Q )\2

=- l- ~------:=-----'EQ -

W=H-l-Fi,

: / J.,

(2)
N __

HF ,

__

'P

' Q = EQ' Q'

F(r) (. ).

Q,

. ..,

'P

(t7,

= l-Fi.

.:

, .
, qt Q
HF .

'P

2
. -
, -

247

 (3, 4) l

r ..

!
2,

4.
2
.

1
02

CASSCF.
K~ CYMMY~H~KOTOPX ,

>-----0

-0,30 L--L-_ _~_ _- L - - - - ' - - - - : - : -

20
60
100
140
180

~ . ,

, ,
.

17.6.

. 17.3.
:

1 _ CCSD(T); 2 - 2

.
1.
.
~
. , 4-5,
.
CISD, . 17.3,
,

3. . 17.3,

(6-31G, 6-31G")

50 - 60 % ,
-0,3 .. (
200 j). ( cc-vZ),
,
.

4. , , ,
. 18.

~ ,

.
CASSCFjMP2

. I
,
,
,
.

2.

. CCSD
, CISD. ,

, . -

248

1.
?
2. ?

3.

I ?

4. () -

5. . 26

(jJt9(at) (jJ22(b 2).

(Ms = ).

18

()
, V,
(..
) .

A7IA

,
(

, ,

18.1.
(Density Functional Theory ~
DF) ,

() L
l.JjI0-

(, )

- ";
1920- . . . .

-'
.
(() ).

- (1927)

m :

"" CF J(r)5/df,
U =.!.JP(r)p(r') d-d-'
2 '-'I ,

= 6

( 3

_ )1/3

41tPi(r)

VX~,J.(r) =6

, ..

().
,
-.
,

.
,
(
, , -,
),

().

, ' - ; CF = (3j10)(31t 2 )2/ = 2,8712.

I:, . m
,
VX<X ()
(1 J,)
1/3:

VXai(r)

('1' I Z 1'1') = ()].

( 3

1/3

4n P,J.(r)

(18.1)

- .
. ill ,

- *. -

(
, ,

,
).
()

(EHF )

2/3

1.

1964 .,
m - *.

* Hohenberg ., Kohn
250

W. // Phys. Rev. .

1964. - . 136. _ . 864.

= +

V,

EHF = + VH +

* Kohn w., Sha L.J. // Phys. Rev. . -

1965. -

Vx,
.

140. -

1133.

251

~ - - l

VH ,

( ) ,

V(f).

Uj

VH ~ ~o, ,

~o = - .

. ,

, ~ ~

,

. ,
J[ , , .:

:
,
-

~I
(18.2)

- .

, .

- (. . 15). -'

(18.2)
- ()] ,

[ ()
[ ()

1 ,
]

. -

V(f),

->

V(r)

[p(f)1 = IV(f){5(f)dr + 7Q[{5(r)1;::: .

(18.2)

(18.2)

+ [p(f)] + ~

f p~~r,;) dfdf' + [()] ;: : .

(18.3)

EV(f)[p(f)] = fV(f)p(f)df +

, (18.3),
( - ~),

Vef,

', :

8P~) [()1

Io[P(f)]df ().
.
:

8F[f(x)] = F[f(x) + 8f(x)] - F[f(x)1 =

()

f ~f(x)dx
8f(x)
.

; ()

= L 1Jj(f) 12.

j=l

(-~Ll+V(f)-j }j(f) =0,

v;,j () = V (r-) + f ' _r 'l d-'r + (-).

r ,
-(-')

() - - , ~YK
.

()

= f fxc(p(f)dv,

fxc(p(f) - , B~ .?
( fxc(p(r
).

,
() =

Jj(f) 12.

j=l

253
252

- 4

, ~

, . .
r, .
.,

LDA

(18.1))
86,

88

Becke
. - 1988.
.3098

. !fJ

~\

(Generalized Gradient Approximation -:-j

PW86,
PW91

-,

[] '"

LDA

38.-

Perdew J. ., Wang . / /

Phys. Rev. . - 1986. 33. - . 8800; 1992. 46. - . 6671

VWN Vosko S.

., Wilk L.,
Nusair // Canad. J.

--

Phys. - 1980. 58. - . 1200

: [] [] -:

. I:I
(. 18.1).

86

LYP

---

)
.

/ / Phys. Rev.

.
.

[] = (){(), Vp(r)}dr,
.

Becke . // J. Chem.
Phys. - 1986. - . 84..4524

G~:

GGA

'l

I'r (. -

.~ - '
(Local Density Approximation - LDA) , (
, 01

LDA

18.1

Perdew J. . / / Phys. Rev.

. - 1986. - . 33. .8822
Lee

.,

Yang W,

" R. G. / / Phys.
. - 1988. - . 37. -

Rev.
.785

- .
:

-1,0269 .. -, -1,0257 ..
' -12,126 -12,148 ..

s(r) =

';~'(~)

- .

/(s(1) :

/(s(1) =

~ (~

~(S(f)2
.
1 + 6~s(f) sin h-Is(r)

= 0,0042)

~ ,
;: -0,8846 .. -11,043 .. .
, , ~

, SVWN -

- . ,
,
.
- L:

== (1

+ 88
+ EcLYP + (1- )E;vm ,
)ELSDA + "rlI JEHF
X

{) =

?'i4

0,20,

0,72,

0,81,
255

, .. .

18.~

RP

,.

-,

, - 1

1726

4243

4142

106,2

-,

MO~_'

2,196

-76,279 0,0960

103,4

1640

3979

3858

2,259

SVWN -75,898 0,0971

105,1

1520

3819

3708

2,214

3LYF

-76,422 0,0962

105,1

1610

3894

3792

2,159

-76,438 0,0958

104,5

1648

3943

3832

1,854

!!,.E~88 -

. . .

* ,

(),
.
,

.
,

( )

-7 .
, . ,
() 'Vi(r) ~:
(,

B3LYP

56

- S,VWN B3LYP (. 18.2,

, , ,

.,

-76,053 0,0941

.
1

- .
:

, ,

18.2.

. ,

6-311++G**).

, (RHF),
, .
,
, SVWN,

N,

)
, (j.!-
; !ly- ). ~

E[{'Vi}' {R[},

{}] = t l d "'V7(r)[- ; : V 2 ]'Vi(r) + U[{'Vi}' {R[}, {}].

, KOTOPO~

(, ,
),
:

!l'Vi(r, t) = -! o'V7(r, t) + I,ik'Vk(r, [),

k

-
,
, .

[[
!ly(Xv

=-v R[E,

(18.4)

= -( / ).

256

* R., Parrinello . // Phys. Rev. Lett. -

"n

1985. - . 55. - . 2471.

257

18.3.

( ). ,
,

. ,

DFT

, , ,

, .

, , *.
.

DF
:
.

18.1.

-. E[{'Vi}, {R;}] .
{R;}. ,
( ),
-

A ik

8( -Il()) = .
Il, -
?
V Il

- ,

Il =

,
.

ll'Vi(r, t)

= .

, 8 /8\jf7

= H\jf7,

(18.4) H\jfi = I.Aik\jfk' -

dEv = 1l8p(r )dr = Il 8p(r )dr = IldN,

Il = (

- . ,

.

,

(~~) )v'

J.

N v

Ili = -Gl

( ni

:
(,

, n;

.
(j",i)

).

- (.

258

18.1).

Langenaeker W. // Chem. Rev. - 2003. -

103. -

Geerling

.,

de Proft F.,

1793.

259

!l -

, , .

, 1961 ., . . .. *
,
N Z:

N-Z= n; = E(N) = n + n + n + dn.

4

-< - ()

n n=

(18.5)

, n = , ~

:
? ,
Pa(r) ,
Q ,
,
', .

\;

. , -;

;
. . ..
;

(18.6)

DF,

.

. ,

=-(~~}

.
, -

, ,
(18.5)

:

(18.6)

(+,

Li+, Na+, Mg 2+),

, ,

(Cs+,

u+).

(),

(N , 2 , -) (-, R-, R 2S).
, . . ,
,

, dE/dN N = Z .,.
. +1
-1 (I1N = 2) I1Epabho-(I + ),

Z-N

-1---.----

D F

. . . . . *

=-

Q---t--=-I

+1----'---

* Iczkovski R. .,
260

..

(18.6).

Margrave J. L. / / J. . Chem. Soc. - 1961. - . 83. - . 3547.

* Parr R.G., Pearson R.G. // J. Amer. Chem. Soc. -

1983. -

105. -

7512.

261

19

, :

S=21~=(:1'
,

19.1.

. (
,

.
(,
, ).
. ,

. ,

.
, .

. ,

(1931). 1t-
,

1.
2.

?
?

4.

DFT?

1t-,

1t-.
:

, 2,,-

~ , ~,
.
, . .
,

, . ,
, , ,

. ,

, .
,

4n

+ 2.

, ( 1950-1960- .) - .

.
, ,
,

.

, , , -

263

- , ~
.

,
.

, .. .

19.2.

-< .

.
.
- (1952)

( 2 r )2n+1
(2n)!

1-'-..:.:~'--_rn-1 -~

MeHT~ H ii
, ..;
i- ,

1
FflV = ~v + I, PflV ([/lv I 0"1:] -"2 [/l1: I crv ]),

(. ., 1960- .)

H ii

a,~

Pflv = 2I,C:k Cvk,

n:- , ,
- ,

,
-

(),

, --
n
(Neglect of Differential Overlap NDO), CNDO

(Complete Neglect of Differential Overlap), INDO (Intermediate

Neglect of Differential Overlap), MINDO (Modified Intermediate
Neglect of Differential Overlap), MNDO (Modified Neglect of
Differential Overlap) .
CNDO (. , . , . , 1965)

. Me~

,

(
,

). ,

NDO,

264

(19.1)

. -

NDO

(19.2)

N ~ .
NDO ,
( )
, .

(Xi(l)Xj(1), i"/:. .

, ,

1960- . m
NDO . ,

8-1/2. ,

,

,
. ,
, :

,
. ,
-

265

'

qB

19.3.

CNDO

= ZB-PBB ,

CNDO/2

CNDO.
1. . Oc~
~ ,
(ZA) .
2.

I1

FJ.lJ.l

= UJ.lJ.l

3. [11111 vv]
, 11 v,
:

[11111 vv] = "{ 11 , v ;

[11111 vv] = "{ 11 , v .
4.

=",,,, +( -~P","'}M + B~ ( -ZB)"{A =

+( -~J.lJ.l } +B~ qB"{A;

11:;t: v, 11

11:;t: v; 11

F",v

~ = UIlIl

L (jll V I JJl = U
..

IlIl -

L V
..

(jl ).

CNDO/2 ","', "{, ..

"{ () ,
. , :

"{

= ZB"{AB'

11 :;t: v; 11

~(1 + O,06945(Y'A RA )2
'

~y =

- "2 ", "{'

"'{ "'{' , ,

",,,,
,
jl
. CNDO/2
VAB

= ",

'

="2 ("'{ + "().

RAB .
,

1
~Y == PJ.lV = "2~ + P~)S",v 11 ; v .

jl

. l1-

S",v -
v. NDO .

5. , NDO,
(19.2).
v,

266

E~ =. UJ.lJ.l

Ne -

+ N e "{ = -",.

267

!J,E

IJl-A,r =-103 +1O~ =-(Ne -1)"{ + Ne"{AA ="{,

U!lJl =

-~(IJl + A,r) - ( Ne - ~ )"{.

19.5.

~1 -
.
; , ,
. (19.1) -
, . 1930- .

CNDO/2

CNDO/2

MINDO/3

MINDO/3 - ,
. 1970-1975- .
;
"{ , ,

UJlJl ,

(,

I', (~Jlv)

( ..:' ):

,
. , ,

(lNDO).
.

I. ([!J,!J, I ] - -21 [!J, I !J,])+ L (

,.

!J, :j:. v

R:v = v (%[!J,v I v!J,] -~[!J,!J, I]}

268

"{

SJlv(IJl

"{

+ Iv) ,

ZB)"{

, 2s (~s)
2 (~p) .
l 3.

19.6. MNDO

!J,

INDO :

FJlJl = UJlJl +

RJ.. + 0,25 (_1_ + _1_ J2

E'j{ = ZZ ["{ + (R~ - "( }-R

INDO

CNDO/2
,
(),

!J,E

= -;=========:='

~JlV ==

19.4.

"{

CNDO INDO MNDO

Xi(1)x/1),

. [!J,!J,lvv]

( !J, , v ) .
22 ( s-) [/lvl(J'!].
.

269

13
-/2

[l-1a]

-/4

13

J[o =

cos ,
V4r;

YioYio = 2. cos 2 =

+/4

Gf)

Gf)

Gf)

+/4

-/4

[Qa~]

(.

19.1.

(-) ,

[flvla'C]

R,
: , ,
..:

[flV I '] =

19.1,

dZ2

).

2
~ [ ~ + v'~)
S 165 (3 cos -1)] =

,,4 ,,4

~ ~( +~Y,o}

z)

, , -

Gf) 2

-/2

131

. ( = , ,

+/2 -ej2 2D, (. 19.1, ).

- .
.

+/2

[q]
.~

, ,

2D2 , ej4.

do.~ (. 19.1, ).

D, D2 :
(. .
,

)
.
(~-
2s- 2-):

:L:L:L[
MI~m' Mfz,m}
1] 12

-.
1

D,

= 5(4~2s~2p)5/2
J3(~2s + ~2p)6

M1,m

21 /2 ,
.

19.1.

s-, ,

D2

="2
(

)'/2 ~21

r:t= ,

,,4

. i,
- j,
:

, ,

(.

270

19.1,

).

271

 Rij ,
DJ , D2
- -

fi(Rij)

N-H

MNDO

: .s, U , ~" ~p, " , .

(19.3)

pf

(l = , 1, 2)
. (19.3)
(Rij = )
= 12.

'!

1=

,
, ,

MINDO/3,
( )
,

. ,

(,
). ,

1= 1

1= 2

, ,
, MNDO, l (Austin Model 1).
l.

cTBo

[Qt'p, Qt'p] = [Pt'pt I Pt'ptJ == h~.

IJ =

12

=
2

[, Mt] = [q, q] = 2~+/2

tr f,; fi ()
2'1 2'2

= 2 (2& )-2 = g;,

& =--

2gss

p~, p~.

MNDO .

I SBSBJ,

~~:

~IlV = ~(~~ + ~~)Sllv'

272

13

( )

19

1989

).

3. . .

(J.J. Stewart)

NDO

(Pararnetric Method Nurnber 3).

. (
, )
. . .
,

Vv~ = -Z[Il V

EX~T = ZZ[ss

.
--

( )

I sBsB][l + exp(-R) + exp(-R )].

, , ,

. ,
,

,
. 03-

~ _ (~ :f): ~~
~p, " /3, ~" ~p, , Gss - [ssjss], Gsp - [ssjpp], Gpp [ ], Gp
= [ j ''] , H sp = [sp sp]

273

, ~
657. .

",

v:, v:, v: -

,
u
u

,
.

19.7. INDO

.~ ,

. '

[/l/ll ]

[/lV IV/l] . '

, ,

( ,
). :,

, ,

' , ~

u ~
, CTPYKTypa~ .

.
* 3d- 4d-
.
CINDO/S

~ 2s- 2- (
).
,

HOCT~

N 2>
z):

3 (

19.8. ~

, . .

-1,5212

-0,7875

-0,5950 -0,5950 -0,5264

, , '

Nl

2s

0,620

-0,649

0,000

Nl

0,677

-0,203

Nl

0,203

0,677

; , ' --
.
' :

Nl

2pz

0,338

0,279

0,620

N2

2s

0,620

0,649

-0,338

N2

0,677

-0,203

N2

0,203

0,677

N2

2pz

-0,338

0,279

-0,620

, ,

v;, = L (-)2;
v;.opc

* Sizova .

274

V = Lke (e- )2,

= L ;[l+s(n-)].

v., Baranovski V./.jj J. Comput. Chem. -

1995. - . 15. _ . 586.

0,338

. )

CNDO

~ ~?
.
2>. ) U 2 2' ?

u

~1

20

5 ,

: .
:
,

20.1.

. ., -;
1927 ., ,
m .
,

: ~

. , ,

, ~
,
rm -

. ,
~
, ?
,
.
(
,

):

, = N[1sa(1)1s b (2) + 1sb(1)1sA2)],

II = N [1sa(1)ls b(2) -lS(1)lS(2)],

; (

) -.

, ()
. .
. IS-0
, (
):

R(r) =

2-

,
,
. ,
.

ls- . ,
,

. ,

,v = N[lsa(l)1sa(2) -lsb(l)l sb(2)].

" , IV ~
, II .
" , IV ~

, -

: ~
. -

N 1/ ~2(1

1
",4n

1
"'n

1sb (1) == _l_R(ljb) = _l_e-I)b.

J4ic

Jn

52),

. :
(

5 = 1):

- lSa 1sb:

1sa(1) == .= R(rl a) = - l1 ,

276

= N[lsa(1)lsa(2) + lSb(1)1sb(2)],

'[

N[1sa(1)1sb(2) + 1sb(1)lsa(2)] .Ji [a(1)~(2) - ~(1)a(2)],

'(s = +1) = N[lsa(l)1sb(2) -lsb(l)lsa(2)a(1)a(2)],

... 'P[[(Ms

= ) = N[1sa(l)lsb(2) -lsb(l)lsa(2)] .Ji [a(1)~(2) + ~(1)a(2)],

'(s = -1) = N[1sa(l)lsb(2) -lsb(l)1sa(2)~(1)~(2)],

277

\f =

(20.1)

N[1sa(l)1sa(2) + 1sb(1)1sb(2)] .Ji [a(1)~(2) - ~(1)a(2)],

(20.1) \fI \f
( ):

\f IV = N[lsa(l)1sa(2) -lsb (l)lsb (2)] .Ji [a(1)~(2) - ~(1)a(2)].

E r, = f '(1, 2) (1, 2) dv1dV2 =

, J

; , . . , Jf
, .
lSa 1sb ~
, ,

~ =

1.

..

\f I \f (~

) ~

, . . ~:

(Lg D~h)' \f \fIV 1

, ..

Lu'

2(1 S2)

f[1s a (l)1sb(2) lsb (1)1sa(2)]

111111)

( -2~1 -2~2 - 'l - '2 - '1

, ,

. ,
lS lSb -
, :

\fIV

+.

-
(1sil)1saC2) 1sb(1)lsb(2, , 2
\f I

(-.!.~1 -l..)1S (1) = E H 1sa(l),

Hb(lsb(2 =

(-.!.~2 -l-)ISb (2) = EH 1sb(2),

,
,

.
,

QK(1, 2)

, ,

278

'l

'2

~b

~a

!:
:

QA

I, = 2 + 2(1 S2)'

= j\f}(1, 2)H\f (1, 2)dv1dV2dcr1dcr2 =

= j}(1, 2)(1, 2)dv1dv2jQ} (1, 2)QK(l, 2)dcrldcr2'

JIsa(1)1sa(l) dV1 =JIsb(2)1sb(2) dV2'

\f .

\fK(\fK(1, 2)
(1, 2)QK(1, 2), QK -
\f ):

Ha(1sa(l =

- () .

ISa 1Sb ,
, :

(20.2)

(20.2) ,
,

,
- .

\f

'2 + '12 + Rab

[1sa(1)1sb(2) 1sb(l)lsa (2) ]dVl dV2'

\fI

, :

Q = - 2f

1sa (1)lsa(1) d
'I

V1

+ f 1sa(1)1sa(1)1sb(2)1sb(2) dv dv + _1_

'12

1)

"

= -2S f Isa(1)lsb(1) dVl + f Isa(1)1sb(l)1sb (2)1sa (2) dV1 dV2 + S2

'l

'12

Rab

279

. . ~.
m , ,

, , ,

( )

Rab

~
,
.
66 % ,
,
. :r

. ,
;

'

. ..

: :'

, - . "
, 1/Rab ( s2/ Rab ) ..,
.

,
: ,

~:

,
() "
. ~ (. 20.1) , -:
, 1,1 .., , ..
- .

Rab = 0,87 (
- 0,74 ), .. -'
U. ( - J
) 3,14 ( 4,7466 ). J

; ,

. -,

, !
!
( ).
.

20.1

, . .

280

Rab

0,5

0,8124

0,6649

-0,2314

0,8989

1,0

0,0958

-0,0897

-0,9965

-0,2952

1,5

-0,0104

-0,1616

-1,1128

-0,6810

2,0

-0,0192

-0,1202

-1,1036

-0,8460

~ , . .
.
,
R , ,
ab

. , HeKO~Opoo

, 1,0 1,6875 .

~ ~

R(r) = 2~3/2e-~.

, .

( ) . (

), ,

~ ~ B~e)
. Rab = 0,741 (~ - 1,1
-1,139 .., 3,782
(80 % ).
~

1! , ! -

2,5

-0,0127

-0,0728

-1,0706

-0,9240

3,0

-0,0014

-0,0363

-1,0417

-0,9626

. ,

, (, ?
)
' . ,
1! (1 ) 1 (1 ):

4,0

-0,0016

-0,0102

-1,0114

-0,9812

(20.3)
281

 , '! ' , ~

lI,g. /.. .

: .
/.. (0,16

); !

'.

. (

= 3,23 ) '
(R e = 0,88 ). i

)
~ ~, /.. (~
.; ~ = 1,193, = 4,02 , Re = 0,748 ).
85 % .;1

'> '

/.. 1 00, 11 - -1
+1; <1' -
( ::; <1' ::; 2n).

. (20.3) ' = ' + /..' (
ls- )
Z, .

, ';
lI,g, :::
'' :: 2 ' - 1 ' -= ' -

/..

, .

1s-bI : 1Sa Isb ,

/3. , , .
,
.

_
.
2 ,
,

, , . ,

'

'

G<l'I

G<l'2

-=---,

'';

_1

L z = -ih G<l'I + G<l'2 '

. . '
<1'2 - <1'1' ,

~ ' , : /"1, 111, /"2,

112, <1'2 - <1'1'

.
, ,

(<1'2 - <1'1)'
,
. , ,
.
v
, v

/"1, 111, /"2, 112, '12,

, ,

. ~
: ,
.

20.2. -
- (l933)

, ,
,
.

282

e- (l+2)
. ~

, . .
,

.
(5, 11 13)
, ( ~
) ,
( 0,03 ).

283

20.3.

, oc~,
, . .,
. . , '

, 4,53 . R = 1,4 . .
(
)

-i

'(l,

2) = _1 e-O,75 0"1+A2)[2, 23779 + , 80483(/-Lf + /-L~) 2

-0,60985(I

, 5599/-LI/-L2 -

+ 2) + , 56906lj2 ].

, . Ocod
, ~
: KOOP~
I, /-Ll, 2, /-L2 (
, )

r- ( ). ; ~OT~H

I .
., 0 ,
-,
~ :
:

. ,
.

~:

.

-- :

. , \:.
, - .
, ~

. '"
- -
: - (
, ), -
-). , ,
.

1950 . . . ,
, ,
- .

.!. [lsa (2) + lsb (2) ](2)

2

.!. [lsa (2) + lsb (2) ]~(2)

2

~ . , ..

.
. .
.

- , - , -
. -
,

,
,
. -, ,
(

)
.

0,5

1,0

1,5

2,0

2,5

R(H-H),

3,0

3,5

4,0

..

. 20.1. , ~eT(~)
- (1, 2)
(1, 3) (2)

285

2R4

 , , ~

, (~

(jg). He~

lI,g. ~

, :

. ,
,

- . ~
..,
,

, ':'

(lsa

.1[\f(lL g )-\f' Lg )] = ',

'P(2 1L g) =

.1 ['Lg )

+ " L g )] = ' '

, , .;

-. ,

~ ~

\f(1 1 Lg ) =

ISa

Isb (j gJ2
= _1_

+ Isb)'

=- 1 (ISa -lsb)
J2

( ).

, ,

-,

~ 1L,g.

(jg ' 1 (jgu. 1 1 (jg~ CY~ 1 lL,u. pacKp~I

, ,
\f(s = +1) \f(s = -1). \f(s = ) \f N
1 (jgu. CY~ 1 1 (jg~ 1 -

"21 [lsa (2) -

1 -2 [lsa (1) -lsb(1) ]u.(l)

\f'(lL ) = g

J2

, ..

lsb (2) ](2)

2" [lsa (1) -lsb(1) ]~(1) "2 [lsa (2) -lsb (2)]~(2)

2
... 3
't' 4

.
-0,4

lI,g
-

. ,
(jg

-0,8

' ,
,
, (
). ,

: \f(lL,g)

_ 1,2 L.J--=:~_-,-_J....---1--'---'----:..L.:::---:'-=-
0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8
R(-),

. 20.2.
( CI 6-3lG*):

\feL,g) \f'eL,g) , .

1 _ 11L,g; 2 - L,u; 3 - lL,u; 4 - 21I,g (

\f'(lL,g),

(jg

286

9.

-)

287

 Lu. , ~

COOTBeTCTB~

21

-.

Me~y 1

AJlA

- . , F.
(

20.2). :

, ~
( ;
l

1
, i!

Lg Iu .

.
.)

1.
2.

- . -

. '( Q, ) -

'JII.

1 <f>Ia <f>IJ) 1 I <2 <2!) 1:

..

J
: : : J'(Q, )* (-L ~A;
+ V(Q, )'(Q, r)dv.
2;
E(Q) ::::: '(Q, )* '(Q, r)dv :::::

22

H12

0,5

-0,40333

3,00719

0,15968

1,0

-1,06600

1,15553

0,17024

2,0

-1,04902

-0,06602

0,20092

3,0

-0,88528

-0,43170

0,23512

4,0

-0,76108

-0,55903

0,26513

-0,59575

0,33730

10,0

-0,59597

l
1

,
'( Q, ) V( Q, )
, ( Q)/aQk

aE(Q) :::::

J{'(Q, )* '(Q, r)dv + '(Q, )* '(Q, ) dv +

~

2,g 212,g.

, ~ ?

~ )
* aV(Q,
aQ

11

4.

+ \f'(Q, )* -'(Q, r)dv ::::: J'P(Q, )

3.

. -

r-

( Q)

, . .

R,

( Q). Q -

'P(Q, r)dv +

Jr'(Q, )* H'P(Q, r)dv + a'P(Q, ) H'P(Q, r)*dV]:::::

Q, S.

aQk

::::

aQk

J'(Q, )* aV(Q, ) '(Q,

r)dv + E(Q,

aQk

f['(Q, )* '(Q, r)dv + '(Q, ) '(Q, r)*dv] :::::

aQk

::::: J 'P(Q, )* aV(Q,

aQk

) '(Q,
:::::

r)dv + E(Q,

) aa

Qk

f 'P(Q,

)*'(Q, ) dv ::::

f'(Q,)* aV(Q, ) '(Q, r)dv.

aQk

rl"I1i1

289

 , - ~
: 1

. ..
,

(21.1)'

F; -

, i- .

,
(21.1)

..,

uu. -"
, -:-i
.

L(-~
a ;)+(V -)1.Jl =0,
;
2; ;
2

(21.2)

, , ,

,
, . . l.Jl .
(21.2) Xj,
/* j:
"
2

"{"( n

')+xjl.Jl*1.Jl-+
aV (V -)jl.Jl * -'} =0.
)
)

.LJ .LJ --/ *

2
) ;
2;
; )

, l.Jl(x) Ix=~= .

L[-~
fl.Jl* ; dr] = _! f'* [L
;
2;
;
2
)
2

~ )~l.Jldr.

J ~

,
).

(21.3)
;

1.Jl*:
(Xi -) 2

aV(i, j)
aXi
,

X) (-

=-[(i- )2+(i-)2+(Zi- Z)2j3/2'

(V

-)I.Jl* = L(~ 2~*).

2;

(21.4)

(21.4)
X;FXi

(21.3)

+ )) + YiFyi + )} + Z;Fzi + zj F7j

= ~"" = V(i, ,

.
, -

290

291

 , , :.

, ~
, ;

xp.l

= _.!.V
_.!.[~
2
2L:-JJ
J

.
. 5

E(R) = D[I- e- P(R-R,,)]2

'

V:!.- ;

D.

D = 4,747

, ~ =

1,9 -l Re = 0,741 .
21.1.

, .

1933 . .
.
,

( ; .
. 22) ,
, ,

, r
2

.=-J

aQj'

, ,

. ,

1 - -1 [ LQj .
T=--V
2
2 j
aQj

.
. 21.1,
0,35-0,40
. 2Re
:
.
.
,
, . -

, .

, ,

V,

12

2\
\

dE
T=--V--R-.
2
2 dR
, = +

..::::::..:::::...

-4
-8

dE
T=-E-RdR'
dE
V=2E+R-.
dR

292

1
\
--- -----\;~:....~::::~.~.~.~:.::.::.::.:~=:

V,

-12

\
'~.. _~i/

0,1

0,2

R,

0,3

21.1.

V (3)

(1),

(2)

293

0,4

0,4

0,3

.",--

0,2

"

0,1
.",

.",

-0,10 -0,05

0,05

0,10

0,15

0,20

. 21.2. -!
:'

p(R) -; 2 - CYM~

; ,

4-

"

"
"
"
"

-,!

''

' ,,

,, ,
0,09

0,08

-..;:

R,

. 21.3.
, - (1)
ro

(2).

-';

Llp(R) - CI

''

0,07

0,06

0,05

R,

1-

""

(. .

21.2,

4;

21.3,

2;

).

. 21.4. R ~ 0,12

, j

):

0,05-1
0,075 , 1

( 0,025 ).

-.i

. 21.2, 21.3. -;
]

0,12

~ . -I

I
I
I
I
I
I
I
I
I
I
I
I

0,08

1 .... - - ...

CYM-j

(CMJ

21.2, 3). - i

0,04

( ) "
(

). , -!

-0,1

!
:<

* . // Chem. Educator. - 2003. -

294

8. -

1.

21.4.

,
\
\

-----/.---

, '
, *.

\
\
\
\
\
\

0,1

0,2

0,3

R,HM

R = 0,741 (1), 1,25 (2), 2,0 (3)

295

 .
:
,
.
(.
.

III.

21.1).

1.
2.

3. (R e = 0,0741 , = 19 HM- 1)
, : )
; ) .

4.

Vj2

22

,
N (
,

):

H(r, R)

MNZ2

f [-~b.A J+ f[-~b.i J-

=1

- LL~+ L~+ L
=! i=1

'iA

i<} 'ij

<

i=1

ZZ2

RA

1' +

( ), -
.
,

. ,

. ,
, .

J.l(, R) -
, EiR):

J.l(, R) = J.I(R)J.l(, R).

J.l(,

-
(R). ,
J.L(, R); ,
. EiR)

R)

(r)

297

 . ~:

(, , )

5,(

x/R). ,
(22.3), ,
. , , ;

'P(r, R) = L,,(R),,(r, R).

"

:
. x/R) -~
. -,
51 . (22.1)

H(r, R)'P(r, R) = W'P(r, R),

vCr, R) 1

= .

. , , ,

. ,

.
,

(Ev - W)Xv + L(v / /",,)

.
(22.3) ,

(22.2).

"

(r, R)
Xy(R). xy(R):
,
,

Ey(R) + ( (r, R) I I (r, R.

,,(r, R)x/R):

.
(. .
), -

(Xi)<
. a~

, (" I V'i,,> -:
. , " ,:

((r, R) I I (r, R

nn

,
.
, . 23.
,
Z.
, , ,

(22.2) 1
,
'

-
.

(22.3)

(22.3)

( - ):
~

li 2

=---.

2 z 2

298

299

=-

Av!!

li [/
2
\ v

02
I OZ2
!! )

+ 2 ( v

I oz !! ) oz ].

, , < )
. Avv -'
-nn ( ),

.~

Av!! -

, ,

, ( ).

. -
.
2 ,
,

, ,

- -.
2 ( ).

~~~~e ~~~~:~~~~~:;~~~~~~;~~~~:~:~~~2~ ~~=~~~

, ** - 2 , HD

,
. . ,
.
, ,

, ,

. ,
,

, .

D 2

1.
2.

3.
4.

[-(1/ 2/l)Ll + U(R) + U'(R)]X(R) = EX(R),

- .

(22.3)
11Lg 2 1Lg ).

(,

:z

(I I 2) I 2

/l - , U(R)
- (.. );
U'(R) - ,

Z, ,

U(R) , U(R) + U'(R)

.
.

22.1.

22.1

112' 1ID 112' - 1

36113,00,3

36 112,2

36118,0

36114,7

HD

36400,51,0

36401,5

36405,7

36402,9

D2

36744,20,5

36745,6

36748,3

36746,2

* Kolos w., Wolniewicz L. // J. Chem. Phys. - 1964. ** Wolniewicz L. / / J. Chem. Phys. - 1966. - . 45. 1()()

. 41. . 515.

3674.

23

.
: ,

.
,

, ,
(,

23.1.

). ,
.

-
, ( Q)
.
. 22,
.
. 25.

. , ,
(,

-) (

). ,

. ,

(~~, ~~, . . , ~~_6)-

,
.

, {}
(, , ):

() == (), 2 , R , ... ,

, (, (, (,

... , qN-6)

, ,

. ,
23.1).

RN ).

(.

(. .

22).

,
N

. :
.

,
.

(J! , ,

F):

.
.

N -

( N -

) ,

F
,

02

 .
.

, ~
nn 3N- 6 (

3N - 5)

.
,

. ,

B3LYP

6-311G*

, (N),
,

+ DE,

'[ (

23.2.

; -

. 23.1. :

33 ).

,
.

.
.

24.

. ,
,

Fd.

, K~K
.
,

(', ' 2 ), ..

Fd ,
(

).
.
d

F , .

,
, .

304

'2'

-
', ' 2 ,
, 2 .
'2, ,

, -

, .

2 =

*[ Wei Z-G., Li Q.-S., ZhangS.-w. etal. // J.

722. - . 139.

l.

Struct.: . - 2005.-

305

23.2.

, OC~OBHoe,

2 I,.
-
.

80"

90";

, ,
. 80" - 3cr-

, 90" -

R
.~

~ 3s .

. 23.2.
, nnu

ssig)

(avoided

2''L, ,

NaCI.
NaCl.
NaCl

( 2 . 23.3, ).

ROHF,

~ Me~

N l
.
RHF 6-31+G* (..
; . 1 . 23.3, ) ,
,

Na+

l-.

-620,8

-621,2

-621,0

-621,3

-621,2

-621,4

-621,4

23.3.

10

l''L, pac~

2''L, ~

.
I ,

(. . 23.3).
,

1 2

R(Na-1),

NaCl,

1 - 112:; 2 - 212:

5,2

, -

q(Na)
1,0

r.:::::
8

0,8
0,6

0,4
.

- ()

306

R(Na-1),

(. 23.3, ).

. ,

, ..

, ,

'(1'1:) = N(3pcrC1(1)3pcrC1(2 ~[a(1)p(2)-p(1)a(2)].

-621,1

, -

, ..

Na-Cl , 6 .

(6):

23.4.

( )

NaC!

0,2

5,2

5,3

5,4

5,5

R(Na-I),

307

~, - .
~ , . 23.4:
R(Na-l) = 5,24

,
q = .

(conical intersection).

.
,
,

'Pr

'Pg.

~=
~ + L (]

- oXi + '"
i

OXi -

aXi

.,.
:

ik + L <'? I I 'PZ)OX"
,

23.5.

23.6.

H ik =

.
(
HNO, ).


,

(.

23.6),

CI.

(-

R ~ FC).

, ,
:

= + ~o [(~o? + (110)2]1/2 = [(~o)2 + (110)2]1/2.

=
! = ~o 2 = 110 (. 23.5). -

308

*, (
) - !
(transition state) TS.
R,
'.

( , ! ,
CI-R, CI-P, CI-P').
.

HNO. .

! 1~ . ,

309

, ..

-129,5

.
,
.

, - ,
. 17.

,
.

-129,6

-129,7

-129,8

0,5

1,0

1,5

2,0

2,5

3,0

R(N-),

23.7.

HNO

, ).
:

C~V. .

23.7

N-H (
N-O ). (

s)
' ".
'()

A'(L\)

,
, .

" ( . 23.7 ).

(. . ), (N - 1)
- .

(. . 24). ,
,
, ,
.

(. .

27).

23.3.

-.
:

! = 21 hii + 1 {2! I jj] - [ij I ji]}.

,
,

. 2
. ,

. ,

310

ij

.
:

= 21 Ghii
i

+ 1{2 o[ii I jj] _ I ji J }.

ij

311

 hii , [

, [ij/ji]

(
),

a
ab

, U

, , :

Ji

I,CJliCVi~V == I,CJliCViJ XJlhXvdv.

Jl,V
Jl,V

h;;
.

ahii = ,,{aCJli .h
. aCVi
a~v}
L CVI"Jlv + CJl/ ~v + CJliCvi - - .
Jl,v

(tj -ti)Ufj - I,I,~,kiUfl

,

L-

= ,ij'

(23.2)

A;j,kl = 4 I k/] - [ik I j/] - [i/I jk],

(23.1)

ij = Fija - S{jtj - IISf, (2[[/ I k/] - [ik I j/]),

(23.1) -
, ,

, .

Fija = hfj + I,(2[ij I kk]a -[ik I jk]a),

, ,
.
:

C~i

= CJli +oaIUficJlk +-21 oa2IUfiaCJlk + ...

k

( )
( ).

(23.2)

- (Coupled Perturbed Hartree- Fock

() equations).

, = . +oaJlk 1 2 2 Jl k
-+- _ __ +
Jl/
Jll

2
2
... ,

. ,

GAUSSIAN)

a CJlk _"
- f Uki CJlk'
2

312

1 ;,
, -
.
(branching space), { , 4 , ... , )
(n - 2)- .

, -

313

 1 .; .
:
1) 2 - [ = ,

2)

_ _
- -

_ _
- .

... -

24

GAMESS

. ,

, ,

24.1.

f
, 4, ... , N ( g).
(1)-(2), G = g + f.

CASSCF,

,
( )

. i :

N ,

=, i =1,
;

. , ,
.

1. .
2. ?
3.

4.

(24.1)

: , , Z.
,
,
:

1

= + I,-dx;
+- I,I,--dx;dxj
2

E(R)

5. ?
6.

... , 3N.

2 ;

j CiX;CiXj

+ n '

- ; R ; N -

2.

, ,
(24.1).

; , . 22 , E(R)
, .
,

, :

(,
; . . 29).

315

,
.

Fij ==

a2V(R).

aXjaXj

; V(R)

QJ.l

2 ; = -J.lfJ.QfJ. == -fJ.QJ.l'

(24.2)

i; -

, i;

Xj, Xj -

a2Q

QJ.l(t) = QS sin(jf;t) = QS sin(21tVfJ.t) = QS sin(rofJ.t).

=m,V, =m

at

j -'

qj = xjJm;. (24.2)

(Xj(t) = qj(t) I J)
(24.3) Lq , , ,
.
()

.f' _

Jij -

Fij

;;:;v;"j

(10.15):

Vmj

= f 'P~ (-)' jd'C = f 'P~i1'P ;d'C,

L q - ,
.
q Q, ij
, :

L (Lq)J.ljQJ.l'

J.l=!

i1 -

qj
Q;

: i1 = ilo + (~~)Oq.

3N

qj =

(24.3)

QJ.l . *,

, :

1 ~2
2. Pk - -

316

,
:

1)
2)

., : / .., ..u,

..u, .. . -

.: , 1972.

;
( )

3)

- ;

317

;
.
3N
3N . ~

4)
5)

, . .

3N - 5)

3N-

~, g ;

( ) (

) . , .. '
-:
, .
(
).
3N - 5.

- j
( , '

, ).

ZO

(I)

1)

0,813

-0,407

Za

(l)

-0,407

(l)

ZH(l)

-0,305

(2)

-0,407

(2)

ZH(2)

0,305

'
- ,

0,530 -0,242
-0,242 0,438

-0,265 0,273
0,242 -0,032

-0,265 -0,032

ZH(I)

(2)

-0,305 -0,407

6-311 ++G**

( ).

, - 1

,
, (
, , ,

24.1

2 ,

0,0005503895

(1)

-0,7527656276

0,5656324605

(2)

318

0,7527656276

-0,265 -0,242

-0,265

0,273 -0,032

-0,032

0,247

0,032

0,018

0,032

0,438

-0,273

0,247

0,018 -0,273

24.3

1 725,8 4141,8 4243,9

0,01

0,03

0,04

4,89

10,05

16,91

2,8

8,4

2,0

0,6

2,1

0,235

0,047

-0,068

0,235

-0,083

0,541

ZO

0,235

-0,067

0,048

(\)

0,234

-0,384

0,411

0,571

(\)

0,234

-0,704

0,664

-0,575

0,538

-0,387

-0,406

-0,571

0,541

Z1)

0,5656324605

0,305

24.3.

, Lq ( )

, .

ZH(2)

. 24.1 .
- 0,941 ,
-- - 106,20.
. 24.2.

L q

(2)

.
. -,

24.2

-0,002

0,235

2)

0,234

-0,384

(2)

0,234

0,704

0,664

0,538

-0,387

0,406

ZH(2)

0,002

0,235

0,575

319

.). ,

Q7- Q9

..

(
, ,

1 725,8

CM- 1). .,j,

, ,

Q7

,:,

(. . '

). , Q7 = 0,1 (:":
, ), Z
( ) 0,0067 (

J ),
Z 0,0538 ,
0,0411 ( = 0,0411),
- 0,0411 ( =-0,0411).
1 . 24.1.
Q7 (Q7 = 0,5)
. ,
-- ( ).
Qs Q9
(. . 24.1).
-.
(

), -
, (
).
L q
.

, ,
. L q ,

24.4

, -

-(1)
-(2)
(1)--(2),

Q7

Q8

Q9

1725,8
0,035
0,035
0,823

4141,9
0,719
0,719

4243,9
0,732

-0,007

-0,732

.
3N -

6 = 3 (
-(l) 0-(2) H(1)-0-H(2,
.
. 24.4
L q
. ,
Q7 ,
.
Q8 Q9 .

.

. 24.5. :

(-) ,
(2,
). , ,
. ,
(
)
.
, ,

, ( )

, .

0,9. ,
( ;
. . 24.5), 0,012. B3LYP

0,967

0,002,

. . -

320

24.1.

Q7 (1), Q8 (2), Q9 (3)

. SVWN 2
0,974 0,948 .

. , 111 11

321

24.5

24.2.

2,2' -

-,

--,

, - 1
l

6-31G

0,09493

111,6

1 735,9

3992,9

4150,1

6-31G**

0,09473

105,5

1826,7

4070,2

4188,3

6-31++G**

0,09413

106,2

1 725,8

4141,9

4243,9

6-31G*

0,09690

104,0

1 735,5

3774,8

3916,2

3L

6-31G*

0,09686

103,6

1 713,1

3729,8

3851,6

3L

cc-vDZ

0,09686

102,7

1658,6

3752,3

3853,8

3L

cc-vZ

0,09613

104,5

1639,4

3800,9

3901,1

3L

cc-vQZ

0,09605

104,8

1633,0

3808,6

3909,8

B3LYP

aug--vZ

0,09618

105,2

1626,1

3796,4

3899,7

SVWN

cc-vZ

0,09692

104,4

1653,3

3733,3

3841,8

0,09572

104,5

1594,8

3656,6

3755,8

VZ
*

: - 0,9066, 2 - 0,9649, B3LYP - 0,9726, SVWN 0,9946.

40 - 70 CM- 1.
B3L

. ,

- , 0,893**.
2,2' -.

- 2,2' - (. 24.2, . 24.6).
,

( , 6-31G* cc-vDZ, 1,0030,009); ,
, 7 %.

* Ha//s , VelravskiJ., Sxh/eg/.. //Theor. Chim.Accounts. - 2001. -

. 105. - . 413.
m
: http://srdata.nist.gov/cccbdb/vsf.asp; http://

**

srdata.nist.gov/ cccbdb/vibsca1e.asp.

322

1,2
1,0
0,8
0,6
0,4
0,2

500

1000

2000

1500

, - 1

. 24.3. 3L (1) 6-31G* (

0,9613)
2,2' -

(2)

. 24.3 2,2' - (
B3LYPjcc-vDZ) .
,
.

,
.

24.6

2,2'-,
(6-2G*)

LVP (6-IG*)

LVP (cc-vDZ)

,
- 1

- 1

- 1

48,0
108,2
177,3
257,2
355,8

3,8
3,5
7,6

58,4
96,8
164,9
228,3
334,0

3,3
2,6
6,4

61,2
96,6
164,9
227,8
333,8

2,7
2,6
6,0

323

 .
(6-2G*)

(6-3IG*)

- 1

- 1

458,9
462,9
(476,7
. 495,3
622,6
674,4
681,8
723,1
826,0
839,0
842,0
859,7
919,8
1018,5
1028,8
1093,1
1097,7
1 101,9
1106,4
1 134,0
1139,9
1140,2
1152,3
1179,2
1 185,3
1 188,6
1213,4
1219,5
1315,4
1325,2
1413,9
1 430,1
1456,3
1589,7
1 617,6
1636,0
1672,8
1 766,3
1 794,9
1 799,9
1808,7
3360,4
3361,0
I

324

9,9

<

0,2

17,2
7,1
15,9

108,9

3,3

8,3

0,1

11,6

1,3

43,0

28,8

2,3

11,0
1,0

54,2

98,9

74,5

137,4

35,6

411,6
418,7
447,1
449,5
572,7
628,4
634,8
672,2
760,1
760,6
778,4
786,0
841,5
922,5
931,2
977,2
982,5
1 012,5
1014,4
1016,3
1 016,5
1059,9
1074,5
1096,4
1121,9
1 126,3
1 181,5
1181,7
1293,4
1 298,6
1334,9
1340,0
1351,4
1465,1
1 491,6
1 506,1
1529,5
1616,7
1635,8
1646,5
1647,9
3 168,0
3168,3

7,6

13,3
6,4
1,8

81,6

1,7

0,3

8,8

0,3
8,1

6,0
16,7

2,1

1,7
6,0

38,0

76,1

39,6

86,7
59,8

,
- 1

412,0
417,7
447,2
448,3
575,8
625,4
624,1
667,5
761,3
763,4
778,2
782,4
849,5
924,2
933,3
983,3
990,0
1009,5
1010,7
1026,5
1026,5
1056,8
1066,1
1083,4
1 111,0
1 111,5

1157,9
1 158,4
1284,1
1287,2
1 329,4
1 330,5
1 336,2
1442,9
1474,3
1485,2
1 512,9
1 608,5
1627,4
1639,9
1 641,0
3149,3
3149,6

6,9

0,1

24.6

L (cc-vDZ)

(6-2G*)
,
- 1

3371,4
3371 ,5
3395,4
3395,8
3435,4
3435,8

(6-3IG*)

,
- 1

3 193,1
3193,2
3213,8
3214,2
3243,3
3243,9

56,0
62,1

1,2

L (cc-vDZ)

- 1

3180,2
3180,2
3201,3
3201,6
3228,5
3229,2

28,6
51,7

2,9

12,4
6,3

24.2.

24.6

22,3
39,4

2,8

74,7
6,0

0,4

(),

S(T) =

+ SBP + S + S

S -- n

15,9
2,3

0,5

7,0

39,7

71,3

39,7

nR[ln(nNo)-1],

R{~ + 1n [(21CMkTJ%
nRT]}
h
2

8,6
9,8

( .

8,0
0,2

(S),

S = nR

'

[~ +
1 ~1C VaVbVc ] ,
2

(j

S = n/~6[ U: exP(~o:) -1 -ln[l- (-u:)]}

S =
() =

nNlnW,

+ + + +

RT,

= R~: =:~::~I:~),
-6

=N I,
:

hv

(:)_I'

91,8

52,5

325

25

25.1.

u
;

n -

hV a
= kT'
R -

; N o - ; - ; k -
; -; - ; h -
'

1 -

() -

; -

~; ga - ; W -

(
, ); - (
).
-7
( - , - )

!1() = Hb(T)-() +-2

L hV a -"21 L hv~.

~EA

( ):

. ,

. ,
,

,
, ,
,

, .

1 3N - 6

=-

2 =l

. ,

hv a

.
,

. ,

(GAMESS, GAUSSIAN

.).

1. 2 447,5 CM- 1

2.
1094,23 CM- 1, 1792,5 - 1 ( ), 3699,7 - 1 3826,0 - 1
( ). .

3.

(. .

4.

24.4).
24.4,

5.

.
- - ( )
.
,

.
,
,

.
. 22.

( ,

327

: -:
, , .

),
(
). fIa ,

, . -
-

~ ,
. ,

, , . {
: -}

. ;
';

.
,
, ,

-'
. :.
, ,

, .

..

~ = - 2n~ [( I ::2 ~ ) + 2 ( I :z ~ ) :z
~ -

. ,
;;

, (

, ).

.

( )
70 ,
. ,
1930- ., . ,
. , .., . .
,: . . . (1935),


.

,
.

.
,
.
He

. (l960-1970 .)
.,-, .., .,

.. ...

25.2.

( ) ,
,
,

,
, ..
,

,
,
,

. , , -
,
, -

328

!l (. .

22),

~ =

ZAe

I, (n
--/: ) - I,I,-+
I,-+
I,
2

riA

i<j rij

<

Z Z

rAB

329

 ~(,

R)

,
, (

). .
.

fl(, R) = flfl(, R)

(
TQPbIX R).

}1

' [(, R)

= I.~(R)fl(, R),
fl

X~ (R)
,
. 1
.
ill

v, fl -

'(, R) = W'P(r, R),

Xfl(R)

( + Efl + (fl I I fl) - W)X fl

I.v (v I I fl) + I.v ~[M (v I V'i~)V'iv ).

iA
1i2

/):

(, I ":: ) = ( , I ~ I , ) /(, - ,)

(25.1)

iA i- .
-,;
!
, 1

. -

. -:
: , .

,
,
, ..
.

, :
U(R)
,
,

. , .
, -'

. , '
, -:

,
. , -\
, . -

330

/
\ ~

= U(R),

umuu (

I d)
;

d)

. -

'P(r, R) -

331

xd

1,6
~
~ 1,2

U+:

= U+(R)X a

'"

tJ
,.:..:; 0,8

V a ( (25.1)

tj
]' 0,4

( Ef.1 Ef.1 + (f.1 I I f.1:

'"

(25.2)

2,0

1,5
.

25.1.

2,4

2,2

(25.3)

qc = 2,07:

1 - a.(q); 2 - sin[a.(q)]; 3 - cos[a.(q)]

. d _ [T~ n + v.d]
d "v.d d
f.1f.1 Xf.1 + kw f.1vXv
Gt
f.1;Ov

lli-Xf.1 -

a(q) = 2:_!arctg [2(q -qc)].

< qc,

( ''P~ ) -(cos
-sin

a(R)
a(R)

sin a(R)
cos a(R)

)('P

arctg [ 2(q - qc>] "" 2:,

W12
2

f)

'P~'

(25.3)

1t

-,
4

W12

(25.2)
(. . 23.3).
(25.2) :

. .

a(q) "" 2:.

q = qc

a(q)

q a(q)

(. 25.1).
. 25.1
.

(~ I :!)

~) + Gq (R) =.

( 1d I-aq
,

a.(q)

'1

n/2

'

n/4

-'Y~

~ ('f + '~)

_l_(_'f + '~)

332

qc -

; W12 -

')

vd

'Y d2

, ,

25.1

J2

'Y~

(v2a v;a J
~(f!Ja + V{
2 f!Ja -

Via - V{ J

v2a Via + Vf

(v;a v{' J

333

 Vf2' ,
25.2),
(. 25.3).

(.

1. :
H l1 =

7L-______J -_ _ _ _
2,05
2,00
.

25.2.

~~

22 = 0,015{[-2(-

_ _~_ _ _ _
,

3)] -

2[-(- m +

0,015,

..

[-0,4( + 4)],

vy (1),

v~ (2)

12 = 0,003[-0,5(-

6)2].

2.
1.
3. 4 . 22, -

(I I ~ 2)
. . ,

. ,

( ).
1
. 25.2

1 = 6.
4. ,

(I I ~ 2) 1.
5.
= 6, 4.

. . 25.3 ,
(25.3),
( )
,

20
10

-10L-~~~__~' __~' __~'__~~

' ___
1,5
.

25.3.

2,0

2,5

3,0

3,5

v1 (1)

v~

(2),

4,0

, . .

-:

(25.3), ~
V12 (3) ( 25)

334

* Mathematica
! .

26

(26.3)

,
.
(26.3) -
(26.2)
. ,

(26.1)

n.
. 5, ,
,
.

= ,

hkot 1

(26.3)

(26.2)

Ll =

..
.

+ Vo(x),
. *,

t =

'w(,t=)=

1
1/41/2exp
1t

[
.]
--2+1kox,

(26.1)

.
,

ro

(26.2)

'(

= (l mro)l/2.

336

Po1 (
aJ2
--+ i[ 4 (J
h

2
2 2 ip ]
_2
_ __
__o_+---LQ.

4 2

2 2

-2iro(

+ ix ( cos rot _
(J

'(, t = ) = (a1t 1!2)-1/2 [ - ( ~a;)2 +

(1ta 2)-1/4

4 2

+ (
- +iPoa)x
- - - -iro( -irot]
-.

(J

'(, t)=(1t(J2)-1/4[_!(~_ cosrot_PO(Jsinrot)2 +

t) =

. ,

v = hko 1 = 1.

(26.2)

. 2
I

sin rot)+ ipoxo sin 2 rot +

. 2 .
2
l

.
lro
2

t]

+ --s2rot---s2rot-.
2
2

(26.3)

* . .,
.: ,

. ., . . .

1981.

337

I 1

iI
iI

1':(, t) 12=

11
11

(j

1 1
1 1

iI 1 1
11
1 1
iI 1 1
11
1 1
1 1 1
11
1 1
iI 1 1
iI
11 1 1

1 exp[-~(x - cos 0)[ - ~sin 0)[)2].

(jvc

1 1
1 1

I \

11
11
11

1 1
1 1

I \

]~ 1 1

= cos 0)[ + ~ sin 0)/,

\~
/
....

(26.4)

-----------------

I~ ;:'-~-==-=--=--=-=;;,.""=-""=-""=-~'i:."'=-'=.'=."'=-"'=-

.. (
) 0).

(26.4).

, ,
,
. :
,

.
, ,
,
.

, ,

, 0),
q
. ,

. 26.1.
()(D):

- t = ; - t = 50' 10-15 ; - t = 150' 10-15 ; - (::: 250' 10-15

q == q - qo.

,
.

(.-

()(D).
. * m
()(D), HDA - 1,4--

. m ,

1,3-

HN=CH-CH=NH

q'l!q

* Heitz . .,
2000. -

338

609. -

66.

+\!-

Guillaumont , Cote-Bruand 1., Danie!

.

,.--....

N N):

// J. Organomet. Chem. -

(500 )

.
26.1
1 '

(dxz ~ c*(HDAB :
- (q) -() (qco)'

':(q, qco). , !l
,
q, ~e<1f~a

1' ( -

339

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

\
.....

//

<.>

'::;: 4
<.>

"'.....
/'"

-:'

.....

"-1

~ 2

O~~~~------~----~

0,2

0,3

0,4

0,1

0,2

0,3

R(Mn-),

R(Mn-),

0,4

..........

/.1'. ."'. .....

11

'::;:<.>

//

....6 4
-:'

2
4

"-1

0,2-------------,

,.' 0,1

.....

(>(D):

"-1

'". _

'--_ _ _'-'-_ _"=-"'"::-=.="-=-=."-=

0,1
0,2
0,3
0,4
R(Mn-),

~"
/."

(1 -

2 - Vg ; - V~4;
4 - V~2); - -

);

(1 -

V14; 2 - V14;

V1)

.
, R(-)

- ) ==
= 2 (. 26.2, ).
.

(.

26.2, ) :
cr -7 n*; V~ - dxz -7 n*; V~4 dyz -7n*.
. 26.2, . ,
V12 -

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

""'~

,t'!~

'::;:<.>

"'.....
/'"

,t'!iI'

~"
/.i'

.....
6

//

2
4
3

i'

-:'

"-1

\
). ,

4-

V?1 (-

//

-:'

(1- ' (

'); -

..........

/.1''''

III

~
.....

JI

); 2- '; - ';

--2-._

26.2.

..........

""'~

,t'!~

~iI'

0,3

0,1

0,4

4
3

\
0,1

" '"

..... .....
0,3

0,2

R(Mn-),

R(Mn-),

0,4

. 26.3. ()
(6) (2-4)
()(D) (. . 26.2):
1 - t = ; - t = 3,6 10-15 ; I - t = 6,510-15 ; IV - t = 14,510-15

dxz -7 n*, ..
Vj,

( ).
,

(.

26.3,

, ,

(.

340

26.3,

).

341

, ..

. 26.4.

2,5
2,0
1,5

NO,
t = (), 826 (6), 4 124 () . .
(z - NO -

, ,

.
:

1,0
0,5

, .

, ,

, ..

2,5

2,0

NO

1,5

( )

1,0
0,5

, .. -------...,

2,5

1. ,
(26.2) ,

NO

2,0

NO ( -
Pt-NO).
+8q,
NO - 8q.

1,5
1,0
0,5

1 2 3 4 5 6 7 8

z,

..

NO

v :
~ (. 26.4)*. ,
, Pt-NO,
- .
~
, -

.
,
-
.
,

i! ,

, -

* Saalfrank . // Chem. Phys. - 1995. - . 193. - . 119.

342

2. : V(x) =
+ 4)]. , t =
= 6?
3. : V(x) =
= 0,01S{exp[-2(x - 3)] - 2[-( - 3)]}.
, t = ) = 6; ) = 2,5?
4. (26.2)
=

[-0,4(

= ,

= cos(rot) + !..si(rot).
ro

,
?

27

qo.
E(qo). l?

E(qo) ~ ~I~
( ) ,
, .

.
,

()

, ,
,

, ,

(.

27.1).
m 1931 .
r. . . ,

.
.
. 23.
, ,
, :

. ,

. Ta~x .~ ~
(Intnnslc ReactlOn dt - IRC).
-

. ,

( ) qo.

qi = m}!2 Xi

5,

,
:

dXk / ds

= gk /

1 gk

1,

gk - , -
(. . 24).
, (. .

) .
,

s-

. 27.1.
,
,

( TS)

344

. . .
, ~

. -

345

27.2.

QST3

( )

Xk

'(

Xk+l

."

, ,

. . . *, ;
.

, Xk
2 (. 27.2). Xk

~ Xk+ 1

Xk+ 1,

1.

Xk+! = Xk - (5/ 2)gk /

()

&:

. ,
-

I gk I .

xZ + 1

1.

, ,

5/2.

,
.
,
, -
,
. ,
IRC, ,
.

.
( l,4-). ,

( C2v ; . 27.3).

IXk+! - Xk+11 = s/2,

. . .

( ).
.
s ( 0,4).
!l,
~,

.
,

. ()
,

g g
g

IRC

. ,

.

QST2 ()
(). -

~ ~

. 27.3. (-) 1,4-

* Gonza/vez

346

.,

Sch/ege/ ..!! J. Chem. Phys. - 1989. -

90. -

2154.

347

0,2

,::;:

==:

~r----------+----------~

~~----------~---------.

19-24-
1,4-

0..

~~

....

::;:

;1

-0,2

0.0

....

~ -0,4

27.1

19

27.4.
1,4-

. 6-31G*.
RHF QST2,

CI.

20

.27.4
,
: , .

27.1 -

21

!
, 2 -

, .

.
;

27.5

250 / (. 27.5).

22

,
.

He !! ! ~ ! (
<1'22 ~ <1'25), . .
.

23

, -

!!,
.

:
14,6 /. ,
,
, -

348

1... a?a'f.b'f.b? 1, ,

24

-n2

349

-(),
/

653

1200

.,~

2
3
4
~ 5

800
r

550

;..

:t:

-::

520

460

(!)

400
.

TS

R*

27.7.

()

(/) ,

246

(. .

10

. 27.5.
1,4-:

1 - IIA 1 ( ); 2 - IA 2; 3 - 2 I ,; 4 - IB,; 5 - '2

-.

37,6

27.6)
/. ,

,
. ,

- (. 27.6):

S. So
. ",
(SO)

(S.)

....:1:...

r
,/

. 27.6. ,

.. Palmer I.J., Ragozov N., Bemard F. et al.(( J. Amer. Chem. Soc. - 1993. - . 115.-

.673.

350

, S,
. 27.1. ,

,
. 27.7.
,

*, TS
/ (. . 27.7)
. /
(2)-(4)
(3) .

351

1. .
2. QST3 QST2?
3. SI

, ,

I ,

SI'

28

f.

14.

, .

,

.
,
, . ,
, ,
,
,

,
,

.
,

,
:
- , ,

, d-d-.
:

,
, , ,
.

BpeMeHHbIe

- (
u ),
.

.

, , (.

12

28.1).

353

, ..

-195,9

~_:=6_-_

-196,0

-196,1

~2----

~------

(
I

-196,2 '--_-"--_---J'--_---L_ _-l.-_ _~

'

0,2

. 28.1.

.
1 '

,
,
,
.

. ,

.
.

, :

. ,
.

.
.

(multireference) (MRCI)

. ,

m , CASSCF.

MRCI

, m -

354

0,5

0,6

Ru(S )( )( 2 )(D) (

CASSCFjCASPT2); MDAB-N, N'--1,4--l,--

0,4

28.2. : a1A' (1), b1A' (2),

(3), d 1A" (4), 1 " (5), flA' (6), glA" (7)

0,3

R(Ru- ),

So

(. 28.2)*.
,
-
(Time Dependent
Density Functional Theory - TDDF).
'Ia ,

.
.
,
()
.

.
.
I
. -, ,
(
) .

. ,
,
, . . .
- -

* Daniel . / /

Coord. Chem. Rev. - 2003. -

238. -

143.

355

 m .

( , )

TDDF ,
,
, ; ,

ce(fb .
I

lB2u

1[

-7

1[*

lB 1u

1[

-7

1[*

lE1g
lA 2u
lE1u
lE2u
lE1u

RYd(3s)

.~8.1

TDDFT CASPT2.
I MRCI 0,5 ( ).
*, CASPT2,
0,1 .
: 8 -

[4s3pld],

6- 8

[2s1p],
13 s-

p-. ,

C6H~

3s- 3d-

()

CASSCF+
+ 2*1 (ANO)

RYd(3p)
Ryd(3p)
Ryd(3p)

1[

'Jc

-7

1[*

4,84
6,30
6,38
6,86 (0,07)*2
6,99
6,92
7,02 (0,82)

TDDF

(6-31 G*)

5,52
6,31

7,38 (0,12)

5,45
6,11
6,06
6,58 (0,013)
6,60
6,66
7,00 (0,12)

4,90
6,20
6,33
6,93

1) 1t- 1t*-
( -? 1t*-);
2)

B3LYP).

28.2

(m , )

()

SVWN

3L*1

(
*2)

(-

pvDZ)

3L

SCI*J

SCI

(-

CASPT2*J
pvDZ) (ANO-L)

1t -7 *

6,16

6,19

6,53

6,45

6,68

6,42

lA 2

6,38

-7 *

4,29

5,07

5,06

6,79

7,34

5,17

lB2

5,43

1t -7

1[*

5,35

5,47

5,73

6,10

6,38

4,86

4,99

lB l

-7 *

4,20

4,76

4,86

6,16

6,09

4,91

4,59

-7 *

4,18

4,93

(SCI)

4,84

6,66

7,10

4,52

4,47

4,69

4,63

4,90

5,40

1t -7 *

4,84

1t -7 *

4,48

3,91

4,02

3,53

3,60

4,1

3,37

4,05

3,98

5,12

5,02

0,67

0,32

0,38

1,04

1,22

. TDDF

CASPT2.
. 28.3 initio
TDDF .
,
.

* Roos ., Fulscher ., Ma/mquist .-. et al. Quantim Mechanical Electron Structure

Ca!cu!ations with Chemical / ed. S. R. Lal1ghoff. - Dordrecht: 1uw, 1995.

356

6,95
6,94 (1,05)

lA 1

1t*- (n -? 1t*-).
(. 28.2)

(

.. Roos ~., Fu!~cher ., Ma!mquist .-. et al. Quantum Mechanica! Electron

Structure
1995 '2 CalculatlOns wlth Chemical Accuracy / ed . S. R. Langhoff. - D d ht . 1uwer
.
.
.
,

TDDF
(aug--vDZ)

, ,

6-31G* , 0,6 .
( aug--vDZ)
.

28.1

-7 *

r'

4,1
0,22

'1 ~HHe .: Bauernschmitt R . Alrichs R. // Chem. Phys. Lett. - 1996. _ V 256 _

. 454. (52111/411/22J' . Sadle'; // . Ch:

*3
,..
,.
eor.
1.
Acta - 1991 - V 79
.
'"
- . 123.
.

357

28.3

Ru(S)z()z(D)

29

Ru(S( 6 s >)z()z(ID)

."

TDDF, L

CASSCF/CASPT2
, - 1

, - 1

, - 1

/(' )

[Ru(>]2+

!!

21260

0,17

22020

0,063

18900

6050

!!

24630

0,005

24680

0,006

25000

960

1 1

29220

0,13

29760

0,042

32260

38500

1 1

32940

0,003

30410

0,01

bI B 1

33930

0,018

32182

0,002

37330

0,005

36540

0,098

38640

d 1B 1

38360

0,13

37590

0,045

1 2

39640

0,003

39760

0,004

38630

eI B 1

uu.

IPDAB -

, CM-1; -

-I,4--I,-;

( d~ 2,2'-

18700

CASMP2?
CASSCF

TDDFT

4.

TDDFT

[Ru!Il(bpY)2(bpy-)]2+.

,
10 CM- 1. ,

. ,

3.

m ,

(Metal to Ligand Charge Transfer - MLCT).

1.
2.

, /(' ); f

(). -
445
d1t -
,
* - 2,2' -.

.
; ~
. ,

MLCT -
(
).


. 29.1, .
. 29.1, MLCT

.
, . . ;

359

. -

. , -

, -

29.1.

Qi):

()
( . 29.1 ). ,
. . ,

. ,
, , (
),
.

1
n1 .

.

(. .

- '/n

,
,
.

:
.
,
. ,

.
,

. ,

,
.

,
)l .
, -

360

=I,I x)e-i,I/n(. 1,

1 .) - .

e-iii'/h

) = ( 1 - i t / Ii -

(1-

, -
, .

-,

6).

iEvt / 1i -

;!

;!

EJt

2
(

n2 + '"

xv>:

]1 ) =

/ 2 + ... J ) =
1

= e- iEvl / n 1 XV>.

I,I .)-t/n( 1) = e-ivl/n 1Xv>,

,
.

,
, ,

361

2:1 (XJ,v 1i,1.) 12 ( v

(29.1)
=
'1'", '1'"', , ' -

f ;

V-

(EJ,v - i,1. =

21cI ei(E-;,)t/n(i,1. (~I XJ)e-it,vt/h(J,v ,} i,1.)dt =

1, .

l..~f ei(E-)t/h(' , e-it/h ' )dt =

2n -<>

1,

f
~

I,

= -2 _ e,(E-;,)t/n(,1,1. 1 1,1. (tdt ,

, ,

(29.4)

, ,

(29.1).

-
Ka-
:

'l'"vih,

(i,1. 1 i,1.(t
. , e-if/h

w=

'I'"~ih

2 1('1'"'etlVI ' et) ('1'"' vih I'1'" Vih) 12 (5 (' - ),

(29.2)

I i,1.) ( )
.

m .

26

(26.4.

. ~

'l'"vih

= i,1.,
j

'I'"~ih = J,V'

(29.3)

. ,

~. -
'l'"iXi, 'l'"J

'1'"/

,
(,
,
) .

(. 29.1, ),
,

,
. . 29.2
, ,

,
.

5i,1. ( ) = 42(/n)
3ch
~ 2"'1(
'7 XJ,v 1i,1. )12 (5( - (EJ,v - i,1.'
-

(5() = -21

j eiEt/tzdt,

362

(. . 29.1, ),

( )
.
, .

363

29.2.

<

I > = { (_OQ2 /2)[1 -

( -irot)] - irot / 2}.

(29.5)

(29.4)

( ) -_ 46n 2
2 n
2

I0- , - 1

] eXP[i(E- )-J{-Sj[l-(-iroj t)]}ctt.

. ,

(29.4)

,
,

(29.6)

,

(. . 29.1, ).

; ,

oQj

(. .

29.1,

).

.
,

.

,

.
. 29.3
C 6 H s -=-=.

TDDF

34482

CM- 1,

Sj

2,5

=~[ M~roj )<OQj)2.

2,0
1,5

oQj

1,0

, ,

*:

oQj =

0,5

(1/5,8065)'L(Lql)ji(roj)-1/2 01j .

0'--_-

50

45

40

35

30

vl0- , - 1

* Myers . ., Mathies R.A. / /

l.

G. Spiro. - 1987. -

364

2. -

Biological Applications of Raman Spectroscopy / ed.

1.

29.3.

365

29.5.

2,5
2,0
1,5
1,0

0,5

18

26

22
E.lQ-, - 1

29.4.

r(N)sN

( =

93

CM- 1)

450 - 1
-- 35200 CM- 1,
- 34600 - 1 ,
,
,

2000

CM- 1

2000

- (.

29.1).

(N)5N (. 29.4).

: =

19500 - 1 ,

,
530 CM- 1. ,

CM- 1;

= 93

,
, ,
,

(.

29.1

(0);) (~;)

(J)j,

366

- 1

(J)j,

- 1

29.5).

)
0"0 .... 1 ( L

CM- 1.

- 1

(
) 400

(1,6), 530 (2,6), 1500 (0,26), 1900 (0,8)

550

= 19500 - 1 --.
.

v = 1

81t 4L
9tz 6c4

II exp[i(EL - ) _] sl/2[exp(-iro/)-I]
eXP{-Sj [l-exp( -irojt) ]}dtl2 .
j

,
,
.

350,994

-0,282

1160,632

0,063

666,107

-0,365

1221,981

0,269

918,093

0,152

1489,256

0,033

, .
(29.1) :

973,638

-0,232

2115,249

-1,161

1010,162

-0,277

2288,491

1,195

367

lnF
-10

O)k, , n
muu ,

- nmuu.
, Ck

-12

-14

k nr - F

-16

= k'P' vib I' vib)

.2

-18

(29.2).

-20

-22~--~--~--~----~--~

10

12

14

16

18

20

k",

+Y[ro.AE~Y[l+ ?1',.( =:

)"''-']]

-l tM )t(ICkI2 k/21i )

= Ft(ICkI2

. - :
l -31,3537 + 1,01281nknr; 1 -

[Re(4,4'-R2-)()1]; 2, 3 - [Ru(tpm)(4,4'-R2 -bpy)(py)]2+

= 298 (2), 77 (3) ; 4 - [()+, [(h)]2+
(

[ -!(1i )]

. 29.6. (29.5)(29.8) -

k/(21i).

(29.7)

= Ru,Os)

( - 2,2'-; - ; tpm ); phen - 1,10-)

mu-(l--

ln knr = ln F + const.

(29.8)

(.

29.6)

2
= [

! (
2
)][ 2 1i j(2 )]l-m/,

+ IQm/

=1.

(29.9)
(29.10)

( ,
); -

; ; -
i-ro

(29.5) .
(29.7), (29.8), (29.10)
.

368

1.

(29.5)

= 500 CM- 1.

t<.Q = 2,0, ) =

2.

(. . 29.1).
3.

t<.Q2
]t<.Q
[---2- (1- cos O)t)(l- cos O)t) .fi.

1.
4. (29.6) ,

. , ?

L(Fl1v - /;0l1v )UVi == 0(11 =1,2, ... , ).

()

=1

(), , i ,

fi , U
, :

("

L(~V - f0!lv)Uv == 0(11 =1,2, ... , ).

(. .

6):
(l)

U.

uu+ == 1

=\

.
F ,
<P11

('Jf =

L <!'!'),

(.. ),

F == LLa:F!,v~;

(2)
(l)

. (!)

U
. ,
.

, ,

!,=1 =\

LIq,1

== 1.

!,=1

F .

all , ,
, () all

, ,

'Jf

(~Ia!ll

== 1).

. m

, , .

F- --

).
(2),

11=1 =1

(4)

La: al1

, .
, (

LLa:F!lvav

11=1

'Jf.

F :
F al1 .

~ :

Fu=Uf.

(11 == 1, 2, ... ,

l1i-ro

a
ll

, -

):

, (4) a ll

(U)I1; ::: LPP.PVi ::: (Uf)!li == LUv.kfki == LUv.kfki = Ul1i /;.

L ~y; == /;Ul1i

(11 == 1,2, ... , ).

=1

370

371

( ~ ~vav )! )
-

"-l

(f ~v
=1

F'bp.V)Gv

v 1 ,

(f F)!v - F'b)!v Ja

v ::::

=1

, ().l :::: 1, 2, ... , ),

(5)

, (3)

U,
MaTp~ F. ,
CMOTpeH~e -::: F

F -

. (5) ~

'
( - 1)
'
.

14, 15, 17, 18

F , ,
,

(
). ,

http://www.webbook.nist.gov/chemistry/

). ,
,

Chemistry Comparison and Benchmarks Database).

Computational

. . , ~
. , ,

; ,

(3).

, (5) ,

(4),

=1

)!=1

2: 2:a;F)!v av - 2: ;)!,

1'=1

F -

,
;

(
) . l. ,

(6)

, (6)

R(C-H) -

(RHF), 0,0017 (2), 0,0013 (ELYP); R(C-F) (RHF), 0,0010 (2), 0,0032 (ELYP);
-- - 0,41" (RHF), 0,58" (2), 0,73" (ELYP).

0,0026
0,0029

l
--

. . (3).

--,

R(-),

RP

3-21G

0,1080

0,1438

109,6

RP

6-31G

0,1077

0,1415

110,2

RF

6-311G

0,1076

0,1415

110,8

RF

6-31G(d)

0,1081

0,1365

109,8

RF

6-31G(d,p)

0,1083

0,1365

109,7

RF

6-31+G(d)

0,1082

0,1372

110,4

RF

6-311+G(d,p)

0,1082

0,1366

110,2

R(C-F),

373

u 2

. l
R(-),

3L

3-21G

0,1096

0,1418

108,6

3L

6-31G

0,1093

0,1434

110,1

R(C-F),

--,

RF

B3LYP

3-21G

2,340

1,879

2,031

6-31G

2,653

2,229

6-31G(d)

1,990

1,715

1,882

6-31G(d,p)

1,981

1,704

1,821

6-31+G(d,p)

2,191

2,092

2,170

6-311 +G(d,p)

2,068

1,884

cc-vDZ

2,023

1,717

3L

6-311G

0,1088

0,1442

110,6

r:yp

6-31G(d)

0,1096

0,1383

109,3

6-31G(d,p)

0,1096

0,1384

109,2

3L

6-31 +G(d)

0,1094

0,1399

110,4

3L

110,3

0,1092

0,1396

110,3

3-21G

0,1093

0,1428

109,1

6-31G

0,1094

0,1454

110,7

6-311G

0,1089

0,1456

111,1

6-31G(d)

0,1092

0,1392

109,8

6-31G(d,p)

0,1088

0,1390

109,7

6-31+G(d)

0,1087

0,1405

110,7

110,3

0,1091

0,1389

110,2

cc-vDZ

0,1102

0,1383

109,3

cc-vZ

0,1087

0,1379

109,8

cc-vQZ

0,1085

0,1382

110,0

RP

6-31G

+325,6

1 125

aug--vDZ

0,1084

0,1409

110,6

RP

6-311 +G(d,p)

+227,6

1223

aug--vZ

0,1087

0,1388

110,2

6-31G

+27,8

1423

0,1106

0,1385

110,0

6-311 +G(d,p)

-153,0

1603

3L

6-31G

-184,7

1635

3L

6-31G(d)

-232,0

1682

3L

6-31G+(d,p)

-235,0

1686

3L

6-311+G(d,p)

-237,8

1688

CISD

aug--vDZ

-50,0

1500

CCCD(T)

aug--vDZ

-209,0

1659

-243,3

1694

-244,2

1694

-236,1

1686

-237,6; -246,9

1 705 15

"

( 298,15 )

,
20 % (

- 1,850 .
, , STO-3G,
15 . 2). RHF

(
).

). . 3, -
.
I -

(CISD).

B3LYP,

174

1,786

G2
G2MP2
G33

, /

375

<:t

'"::r
=:
r:::

'"
f-<

.~

-:-

....

-"

"=-""

"~

8
::--..,
::t::a

":Q
<!)

Qj

s;

,~

Qj

"")

~~

:I:
:I:

(1j

"1

'"

r-;,

-"
::--;,

t::

"")

","~

==
:r' ""
==
Q ""
~

...

Q.,

"")

.....

0'\

..... 0\
..... '
..... <:t'
..... .....

.....
<:t

.....

v)

0'\

.....

00,
r')
r')

v)

1:'-'

1'-'

"")

"")

<:t'
<:t

v)

.....

N
1:'-'
1:'-

N
'
0'\

<:t

\,

v)

<:t

00,

0'\

,
\

.....

.....

00

1'-'

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

~::;;
-"

;-'",

0\

r-;,

v)

v)

1:'-

1:'-

00
00

*l
()

-,

HF (STO-3G)
HF(3-21G)
HF (6-31G*)
HF (6-3+G)
HF (6-31G*)
HF (6-3+G*)

1,750
1,825
2,026
2,014
1,959
1,930

, /

-24,79
-45,90
-23,53
-22,51
-30,60
-29,30

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