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26
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30
31
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4.1.'V
f(t) = const e-it//i.
~~ ~ Me~
, J,~l?~ , ,' ,
, . q-; d
(. -' . , -
(2.1: .

n <n(),
i1i '(, t) = '(, t), 'n(, t) = <pn(x)f(t)
at

'(, t) - ; -
'Pn(x,t) = <pn(.~)e~iE,;t/~:
, '; t - ; - ,.\3 F,
. BpeMeHJ4:. 0
' n(, t) , 'l' , :
, .. '(, t= ). u '
, l : -;
,
F = J'P~(X~ t)F'Pn(x, t)dx = J<~()int/IiF<n()-int//idX =
q . ' = J<p~{x)F<pn(.i)dx.
: r I.
, - -; , t ( ),
, . :
(2.1) ,

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 < () n
n

34 35
 . ,
-
!n'n(, t) = LCnIf'Pn(x~ () = LcnII<pn(x)e-int/h = (,. il , ).
n n' 'n - , '"
= L...-
~ {n (X)e-int/h
n n"t"n ,
.,
n
. ,
. :
. , ,

"4.,Z. , u . ,
1 ,
. , ~ ,
, ;, o~ .
():
H' .

M2i~' ( - = f ''* (. ~ )2 'Pd't. ,

; ,
., l'
- ,
~, .'
,

- -
4. : ..;
~ ~
~ ,
(4.4)

.
, I () -. ,; " = i(xp x ~) = -1'1 ; 2 ; ;:: 1'12/4.
'1
~ ! > -,~ t ,
f (*'* - i.*'*)(.' + i.'f!)d't = f'P* / + /2 .
'Pd't;:: (4.21 .
, .
~I (4.2)
:
,~ ' . , ,
- 0,529 10-8 .
2
f'P* A2rd't + i.j'f1*(. - EA)'Pd't + ,2J'* E 'Pd't. (4.3) ljepaBeHCTBa,

= -). -: ;:: 1'1/2.

:


2 + l + . 2 .2 ~ .
. -I - 1'1 . 1,054.10-27 11 108 /
, ' >--= "" .
V_ .:..' 2.9108.10-28.0529.10-8 ' .', '
2 '
,.
,
1/300 . <
13 m .
, : ().

36 37
 () t.[

II ' I
, , .
(4.5)
, ' .,
, . (

" ).
.
: -
.
- " . ': :~.',
. , ,
t . Pt= ln dt (, ,
, . . ,

. ':,,
, ,
, . :

" ~ :

t(i1i
".
J-
d (i1i d')t = i1i.
t ,,'
CJ dt
.

'

. t ; =in :t (4,3), -1. lf~ ~ Ce i (p1)/h (

) .. , q, 9
. ., "
2. I~ :-
f'P*t 'Pd't + i'*(ft - ptt- in)'Pd't + /..,2f (! ') * (! 'P)d't ::::
2
/6 '?, . ' . " ' , ' .. , "' ,

3. i.~ C\<I'\ + ~2<1'2 2<1'\ - ~\q,2, ~ \

f 'P*t 'Pd't + '*i(tt - ptt)'Pd't + Mf~~'Pd't -: /..,2 f <! ');*(! 'P)d't.
2
= 2 i, lf <1'1 <2 - .
4. . jj =-0,3 /2 =-0,77.
! , ),

\jI = \<I'1 ,il/,h + C2<1'2 eo,77it/h

(<1'\ lf <1'2 - ,
jj /z) .

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

6. F i~.,
= (! ') ,
- . \jI(x) = L,Ck<l'k(x)e-ikf/h, 1 , -
. .... ' i "
, pt'P = '.
u
.

t t
-to, Jj - , -
: . '1'.
, = '! - ptt)
n,

38
 5 'I'(a) = sin(ka) = . , ka = mt, n -
. n ,,;
,
'.
n; ,
sin(-mtx/a) = -sin(mtx/a),
,
. , n = 1, 2, 3, ... '
I;i :

, c2 1i 2
: n = - 22 n2 , n = 1, 2, 3, ... (5.1)

,
'. : , ,
: , (5.1). n
,
, , "'" .
.
yro .

(. 5; 1). ,
= 21 sin 2 ( nr)clx =J.
",
< < ( ) () ,
( 1, I) () = 00.
tf [, ],
1air 2/;
:'f() =0" 'I'(a) = .
, 2 = /2, '
, , II , , ,' "', "
ri'd .
II ~'' i -
.: '

. 5.2 ~ ,

. ~
k 2 = ,2
2
Ii: ,
1i , 9 'l'n(X) ";0
~ B~y n- , : q ,
~~ , -

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

, lI
1i - n -n - 1 = E 1(2n - 1). .,
1 11 111 : , ~
jf. '
. 5.1.
'I'(x) = sin(kx + ). , .. ,

,
- '1'(0) =
,
. .
= .

40 41
 =

"
] ]
=
-
..
1 II III ~.

. 5.3. fJ<:\ iI

~ ( III). ,
I 2, = .
,
Ix ~. , ~ ~
; 5.2. , I1 n = 1 ;'
(l),2.C2), ~(); -!lJ;.I . I. ,
.;'.(
;, , ,
. .
, (, ,
, ( J:l ). .' ,'" . .
) (n - 1) . u II '
, :
r.f .:.
<),:~ u u
.

.
, , , , ,,2 = 2
'(/ = 1/2). 2 n
'V2(X) , = /4 ) = 3/4, '
= /2 .
, ' 2'V() __k 2 . ('.' )
, , , 2 "'- 'v .
' ,
( ); , 'V() = Acos(kx), -
, . ' u ( 'V() = Bsin(kx).
). 1I , - III:
J.r = /2. '
, ,
: u (. .
).
. "
, ,
, ri
(. 5.3):() =
- << ( ) () = ~ ":' ( 1),
43
42
 .
. t.J: ,
.

. -.rp
' . + ,
, .
'J1r{) =
-. 1 , 1 III.
, 'vix) =
, + ,
re CCOOTBeTCTBY~T! ~;e'p;iI,' 11; !i:~ - - . .
(j; :,, I~I ..,
, ~. II~ .. , !i,Iirl' 1 III .
q =. ffl ",(.) '''v~() . ,
~ s:rI.I? - ~
~.1': : ' , n. ?
-
",iI () . ",i() .
",() = /()
1 .. 36 .. (
"'() "'() , I:' . 8). . 5.4
: ~ , , ". '
ktg(ka) = '( .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 ..
; . 5.5.
kctg(ka) 7'.-'{',
- . fJ
'(2 = v 2 - k 2 , (
Ixl ;?: aj2) .
ktg(ka) = .Jv 2- k2, - kctg(ka) = .Jv 2_ k2 (5.2)
(5.2) -.rp

. ~ 14
jJ v ,
12
'( = ktg(ka), '( = -kctg(ka).
10
8
6
4
2
n - (
1).
, Ie Ii
2 4 6 k
! < 2 < ...
, . 5.4.
. : (v 2 - k2)!/2 (1), ktg(ka) (2).,
, - -kctg(ka) (3) k.

44 45
 \
'1'" / 10- 1 = 2n (n = , 1,2, ... ),
1,2 i
"
.. Pt;tm Hn(~). "
(5.3)
0,8

0,4

" - i .

-0,4 q n:
-0,8 '
. .~"!

-1,2 L-~~":'-"';";"';'J..;.....O,----"J--':;""":"'-";"""--"...J..---'---~ " \jfo(~) == 1[-1/4e-:~2/2,

""11~5 ,J,O ' ::;-0,5' Q 0,5 1,0 1,5'
\jfl (~) = 1[-1/4.J2e-~2/2~,
., 5.5. ~ \jin :(;"*~fI =' 1 (1), 2 (2), 3 (3)
:i: == l' . : ( \jf2(S) = 1[-1/4 _1 e-~2/2(2 -1)"
, , ;iIe 1) ,; .J2 '
\jf (~) == 1[-1/4 _,
1 e-~2/2(2~3 - 3~).
IIJ. r: , ..r
~)) 7 ,
(:) = mro 2 2/2. ~ 1<; ,

. ~ : ,
I:Q ::, .,
\
," ' ", ro ' ,'" "
, 10- 1 = 2n = --, -
2 '
,
-
\; :

" =ro( n+~)= hV( n+~)-
, ro 21[, v - ~
(5.3) > . mm ,
= ro/2.
, ~ - . , , -
~ ,~ ~2 .
. ~ ~ ~ 00 . -
\jf(~) = e-~2/2. ' (5.3) -
(. 5.~):
"
,

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

V(x) = (-2 - 2-

),

= R - Re (R e - );
.
, , : , :;t?
, ( - 1). . . -

46 47
 v, -. a(2Ajm)1/2
4 1
-2
\jIi
.. ,

1,0 .

, ,
2 "'4
, , ,
n.

. ,
. 5.7 t5t
-2 2 , .'
-1,0 , ,aJi,:l;r
-4 (-0,054 ) n = 17. , -f';
, 0 n.
-0,1 -0,5 0,5 1,0 1,5 2,0 . 5.8
R-Re , .. , ~~

. 5.6. (1)
>~ . n 2 =
-0,0005 . ,
=
: n (2), 1 (3), 2 (4).
6 . .
=
; ;:: -4,747; -4,475 ; 1 -3,954 ; = ( 3,2 ),
-
~ = .,...3,466 ; == 2 104,7 - 1 ; 1 - = 4195,0 CMc1 ; ~ - 1 = 3935,9 - 1
-101 ' .
:
. ( = " ,
V(O) = -), ~ 00 , :.. ' '
. (: . J! .
: t). 'f
, '
\ (,

n '=-A[l- ~~~A(n+~)J, (5.4)

-J1 .-

\jIn(~) = e-~/2~s((~). ,
1

--------------------------------------------
): = 2,J2mA
~ ,'
-
-~
"
<,): < 00'
,
-1

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

-3
- . M~cca '; (O(~) == F(-n;'2s+ 1, ~)
n
-4

-5
( ) 1 z ( + 1) Z2 1,5 2,0
, "(, Z = + - -1' + ,,( 1) 2' + ... -0,5 0,5 1,0
, 1 l~+ . R-Re , ..

. 5.6
,-'. 5.7. I 2
( ) 5'
( (5.4
n=
, 1, 2.

48 49
 . ,
.
2,0
n

'Pw/X' t) = ] C(k)'Pk(x, t)dk = ] dkC(k)eikxeink2t/2m. (5.6)

C(k)
= k1i .
, ,
, .
10 20 30 40 50 60 70
, C(k) k = k o
. R":"Re, .. Bl:fe

. 5.8. (, )
n= (1),
1 (2);,2. (3)
C(k) = ~ 2;/2 [-
2
(\- ko)2 J
(5.6)
).

Ml;{OrOaTOMHbIx , ,{ -1/2
::

'I'I .
'l'wp(x, t) =,n [(1+ 2 J]
1
1/ 4
i1it

l ~ : OJ .
'IIt~
, 'I I:I \
-
( -hkot /
(
)2k i1it
iht) + 1 - 2 2
1

(5.7)
0 '{I:I - Q .
'I
(V(x) = ),
l 2 2 1 +--2

(5.5)

'1' k(, t) = e-it/h/kx

. ,

= hkot/ (5:8)
. ,
h2k 2 v = x/t = hko/.
=- . , -
2 '
(5.8) .,
k - ,
k = /h. ,2 2 )~1/2
, , = [ (ln2) ( 1+ ~2~4 IJ'
, Qrp -

50 51
 'P wp :
0,6 ct , -
. -.
0,5

0,4 *

0,3 1.
0,1 1
0,2 : ) = 0,5 , n = 1; ) = 0,25 , n = 4.
-~
2. + 1 - n fI
0,1
?

3.
1,5 .. 5 ...
-3 -1 2 3
4. = 10 , . = 2.
5.
. 5.9. .
= 2 .., . = 0,01 = 2000 ..
6. =4,76 , . = 1,05.
. 7.
, I;I.
= 4,76 , . = 1,05 = 1000...
. , 8. .~ () .lIO
t m 2 / n. ~ ~I. KaKO~O l 5,!/3() ~
, vt = koa2 l:j' ?
(5.7) 9. . ,
(5.5). , , ? .

.\

. ,
n2k?; .
, (
), , ,
,

.
=
vt, ,
; ,
.. , Q;
., .l ..,
.
* , , -

4 2
. ._
(l . . t;2 = l1Q = 27,211 , 1 .. -
.
2 . .
, Q
~ = O,0529177~M ) . 1840


. , . . 1 840 . .

52
 " : 6 ,
'(). {ai} ct
'().
L-, BJ1Y, () -
BJ1e L,
.
{b i } :
()' L-. ~<x), () -
, :i ~ : KOOP~Ha! :
~! '() , - ~ , :Ie KoopQ?l:HaJrJ1:IOM :"
, . ": , . -.'
I1 ~ , : ,. ; ~
L, <Pi(X).: . ,. i

'() =2A<PJx).

=[:~. ]; =[~],
i
(61)1
, ~
:. ,
.I .' ?,. . . -.
. , . '.. . ..
v
L, i q./I : :, : F;k == <p;(X)F<Pk(X)dx 'j. J

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

t (), R -j
\ Fi2 Fi
F '(): () = F '(). ! F= .F21 F22 F23
<Pi: . Fl F2 F ""]
'" ,

() = 2:bi<Pi(X) = 2: ; <;().
i j (6.2)

~ ; , ,'
: -.
bk ='LFkiai (k =1, 2, ...)
i
<) (k = 1, 2, ... ) . :
. b :
i

B:;;.FA
; = 2: ; J<Pk(X)F<Pi(X)dx == 2: Fkiai (k = 1, 2, , .. ). (6.2)
i i , ( () L-)
( '()! -
'() =2:ai<Pi(X). , -: ), F (
. i "
F), F
(j>i(X) 1 . , F L-. ,
ai, ~ '()
{}, . . {ai} -, () = F'()
54
55

J
=F ;j Fi2
F22
Fi
F2
... ]
...
2

, i F :";
'I'(). j F2 F .' .:.,~. ".
F* , (F*)ij =; n'L,:
~ F; , ~i
I F : . = F ... ,
(.4).
!l F+,~+~~ ~ (F+)ij= (Fj;)* ~ M~;~J LB

, F. (F+)ij = Fij , F
n:>f:~ ,um. , ~ L-: '
:
(5.1). ' 2

L = l:l:a7Lijaj =2, lil aiI .
i j,
, .
KpOHeKep~ I;I ~
0ik = 0k: Oik = 1 i = k; Oik;: ri i::f::. k. '(): '
j! .
L . f:r*(~)'P(X)dx = 1.
Lik
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 =
J'I'.,. *()'I'()~=2, 2, a7ajJ <7 (x)~j(x)dx= 4,lp;( == 1.
= IkI <r>7<r>k(X)dx = lkoik' (.3) 'i j' I

, , L
.

( )
F. ,
F
:

F =J'I'*(X)F'l'(x)dx, (.4)

F - ( )
F , '1'.
, I1 L- ,

(.4) ~: 2

F = l:l:a7aj J<7 (x)F<r>j () = l: l:a7 Fijaj + = (ata2a; ...)
i j i j

B - ,
v

5
57
 . . ;

2 F . , L.,GI, . .
Llail =1. ; QGr
Z.
: , B~
<1'/1 ,
'1';, ,
~e ,
:

F = Llail2Ji, '1'; = L. </1U/1;'

i /1

I' Ji - ~:';I . , ' U,

'l'i m l>r:
~ ~
, . Ji, TOjj
, ai co~ f 'l'i'l' jdx ;= L L (U/1; )*Uvj f <I'~<Pvdx =
/1 ' v .
I":Ji ';I':
. TpaKTOBl1,j = LL(U+);/10/1vl:rVj = L(U+);/1UW = . (6.5)
(:m; . , s; /1 v /1
< U+ - , U: (+);/1 = ;;.
! ,l;j. :
Q . ,
, ;; 'I'=<pu,
.: (6.6)
",+'1' = U+<p+q,U = U+.-:=: u+u;, ;
, ~ Ji;
, 1 - , ~j == oij. .,'
I ~ , (6.5), (6.6) , U+ - ,
9 "' U: U+ = U-l< , (
. . I -
",. ),
;, , );,. .(;
Jjl i.
Q~. ~

F
', J
: 11 1 ),
. ~
, , F;J'J!) = f'l'tF'I'jdx= LL(U)~;VjJ<I'~F<vdx=
/1 v . . '
, : ( 1.
~ ( i = LL(U+);/1~)UVj = (U+F(<I/)U)ij
/1 v
bracket, , ). ( 1 ) .


(6.7)
J
('1'; 1 '1') == '1'7'1'jd't.

:/
n
. , -
,' F('J!) -

58 59
 Ii
, I
: Fjo/) = /;: , ~
F:
x+r02x=O
. (6.7) ,
, ; ") mn
( + )2mn -- . (6.9)

SpF = LF;i' (3.5)

;=1

~ '.,.....
=- ( -
.,.....
). -
l, ,
,
S
(6.8):

" P~o/)
SpF(o/) = LJ 11
;=1
= LJ
" LJ "(+).1/.1. F.(<P)U
" LJ
;=1
~y
~=1 =1
VI-
- ()mn = -i "2JHmk Xkn - XmkHkn) = -11.i (Erxmn - mn n) =
11. k
.

=LL~~<P)LUv;(U+);~ = LL~<J)I~v = =!....(m .,... n)mn = ')mnmn'

~=1 =1 ,;=1 ~=l =1 11.
.
=L L ~~<P)O~y =L FJ:) = SpF(<P). 3fI()~n = ')mn()mn = -ro;'nmn' ,
~=l =l ~=l
(6.9)
.
, . 2 2
() -:- )mn )x~? -- .
:
,, mn -
.-. . d 2 0)2
2
=--....-+-- 2
(6.8)
.
, )mn = )
2 2
,
2 dx 2 2 . , n
0)11.. n ,
WN
n =
nn . ,
, .
(6.8) , : , KOTOP:~ . .lf~
2ron, 30)1i,4ron, ... , .,
; = i: = mi ( (r02 - );'n) = ,'
),
n n'
Ix
' . -
.
, ,
F =
= jJ == -vv
mn : mn = nm ' .
;
n1'
mv = =-VV. n
,
:

2 . . = -1-.
.n
V ----
) 2 -

2
61
60
 ~
, ( ,
, nm = - mn : , .... , 1
1.
" ~

+-n
2
0,64.

.
2. :4, <!,
,
<2, <t',

, r

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


3. :4, . 2,
,
.

, n,
. ,
, lI n .
-1
, ' (l 0)2 = iz/(2). . 2
, , 4. 1'~ -K~
, " n' +3, +5. \ ,
(n n_l)2 = -2',
, '

[
'40]
n , n-l
.
= Xn~1 ~1i
. , n = -2'"
.
(6.10)
0,70 .
0,59

5 =: cos2e (
~
;). -
:
~

= '2 )2 + 2 2
).
: ) ,1; 5) ~ , ; ) os' ~i).
r. <; 6. V
4n s s <t' -
r (6.10)
, '

;
-
81t
.
s <
i'i'

, . 5.
62
 ~2
7 /
,
:

~2 ~2 ~2 ~2
/ ::: / + l + /z.

7.1.

~12 ::: -n2'\162 ::: -n 2 -,--
'1' sin
[1
(,s-.
. ) +--,-'.

J'
sin 2 aq>2
1 2
(7.3)

-
~ : 1-!I
, -

1 ==. , ( -)::: i/i. , ;-

[, Zy:

/ == : - ZPy, / ::: ZPx - xP z' /: ::: - ' ;.. . . - 2 ..... ",2,,-

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

~'::: -ln. ( )
_ ..... _..... _..... ~

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

dZ '

.
~/::: -ln ( )
Z--x- (7.1)' , lx,ly .
(jz' ,

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

[/x,ly]==in1z,
- . [/z, lxl == ihZ y , (7.4)

[/, lz] == iliZx.
,
.
(7.4):

~ ~2 ~2 ~2 ~2 ~2 ~2 ~ ~ ~ ~ ~ ~ ~' ~ ~ ~. ~ '

(7.2) /x(lx + / + /z)- (lx + l + /z)lx ::: lx/yly + /xlz/z -/// -lzlzlx =
::: (ihl z + lylx)ly -ly(lxly - i1il z ) + (/zlx - i1il y)lz -/z(ihl y + /x/z) =
= 11i(IZly + //: -Iz{y ,. -Iyl z ) = .

64 65
3
 I

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

[l,Zx]=O" o (8) = (2/ + 1) (l-Iml) !p,lml cos 8, (7.7)

2 l, 2 (l +Il)! '
[l , Zy] = ,
2
[l,lz]=O. ~Iml cos 8 - ::
(
<: QR , 11 1 d l +1ml ,
2
' p,lml cos8 = -sin1ml 8 , I I (cos 8-1).
, 2'/! (dcos8)+m
, . 2

: : . , : (7.7) 1
, - Z, ( ):
, z
.

7.2.


", l, ~ ;
2 =' (-1), <.
{
m , 1 lz , I'
~. .. .
(7.8) (_1)m ~
1z
L;
(. 2): . ~
1e1m'l'.
. , ,
(
<)= __ , e~. .
.. ~ .';I / = , 1,2.
2
1
1
",(8,<) = 0(8)(<). , = .n'

yi
, = V~
cos8,
z 2'"( .("s 8 ",(8, <) +. -12- ",(8, <)] =
2
< ) -_ -*-2 [ -1- -
-3.
~81t
, sin 8 8 sin 8 <2 8' ilP
yi ! = s ,
, (7.9)
== L1i 2",(8, <),
2 i 2 = {5 !(3cos2 8-1),
L1i2 1' , V~2
( 1i 2 ), j

~
+.
0(8): 2 ! = - . 3sin8cos8e-I'I',
, 241t , .

_.1_~(sin8d0(8)+[L_~0(8)=
s 8 d8 '. d8 . s 2 8
. (7.6)]. :2, 2 = J 5 3. sin 2 8e2i'l'.
961t

66 67
 ~2 ..... ,,... " / . >'
S ,Sx,Sy, Sz. I>I
s, , d ., '] , I :~{ .
, . >'l;{ i
2 2
S s(s +1)/i " S = 1/2,
Q
. , .' 1 ' . ".
s - 1 Sz -'- ms/i
.
= ..:../i
2 '
. .

:.,1: r' Sz m.() , ($ -

, +1/2, -1/2. fI-
z
: " .
d 1 J
dz; -(3z2 - r2 )
2 \
l/2 (1/2) = 1, .
, \ :
' dx2 _ y2 .J3 ( 2 ;,.. 2)
~~

.,' 2 '
.j
..~ -l/2 (1/2) = ,
, '.'
dxy .J3xy ~
112 (-lj2) = ,

l' dxz \ .J3xz -:-l/2(-1/2) = 1.

dyZ .J3YZ -'1 I;I<' XJj2 (1/2) -l/2 (-1/2)
. ~ ;
(7.9)
, , , , :i :
, d . , .
. ( ~:
(7.9). t~
, ' aj .. cr=I/2
: f (X~dcr
,
-7
cr=-1/2
L l/2()-l/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 <, j , "

'
z =r cos , . Sz, .

., +1/2 -1/2,
eimq> = cos(m<p) i sin(m<p). ( ~ .

,
( 7.4.
, ' : 1),
. 7.1. IyI: . . ,
He~OTOpoo .

7.3. v
m

, ~ 2
, l\1 1 lz. ,
- . o~ , ,
s. , " " pal~oo ; -

69
. !?, ~ "' [}+' }z] = -0+: ,( I

(, ). .;;
09 KO:d [}+,lz1\jfm = j+jz\jfm - jzj+\jfm = -f+\jfm.
, , ,
. ~ ,j
qr , KOTOPI;>Ie m ,
"' }z
( , : ,

"k{ . z..
-i }zO+\jfm) = ( + l)(}+\jfm), '
, :iP~ l1ui~:, i . :. , ,
j.
, $l , } + "',
(. } z , ( + 1), -
2 2
.
, s j ). "'+ 1 , -
yti : :

[}, f y ] = ilifz; [} fx] = i1ily; [}, fz] = ilifx (7.10~ . (7.12)

m J , j+ yio
I , g
.. 2 :,J \Vm ,
1, , .>q , ()
: : . , .
2 2 ";2 , IM , , nuu
[j, jx]=O; [j, jy]=O; [j, Jz]=O. (7.11~ f_, ~a "', \jfm-l:

j+=j+
'" ,.. ,..

i_=jx-ijy .,
,..
} - l; = bm\jfm-l: (7.13)
.' .

; j+j_

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

j+j_
,..

= +) -ijy) = jx + jy +i(jyjx -
..... 2 .... 2 " "

jxjy) =
[}_, }z] = [}, }z]-ir]y, }z]"; -ih}y -li}) = Ii -~y) =Ii}_., 2 2 2 2

= j + j - i(ij <) = j + j + j <'

[}+,}J = +i}y)Ox ~i}y)-Ox -i}y)(}x +i}y) =
,
, .~ 2i(jy}x:'" }xly ) = 2tz}z. '2 2

, , 2 '. j == j+j- - jz + jz
, j+ j_ j .
~ i~ } <. : ~
,

2 2
"' , l': r4
j =j-j++jz+jz
,} :

"'.
j z\jf 111 = ",
.
( , Ii = 1).
71
70
 . (
I<:
, :

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

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

\jI ,d't ) * .
, I
(::: j) ( = :"'}) :0
Z : . ,,;
' = + 1, , ' ," ;'-" '

\. ~,., ' , :. '. ~ . '-,' *

7.5.
J\jI~+! ?+W!1Jd~ = =(J \jI~) _~+ld't) =:I+!' .!,

:
d; 't~ 13
. , N:
If ' "' q
. ;.,.
.
2 . . . ..,'
], , . ' ji (i = 1, 2, ... , )'
' j!(j! + 1), j2(j2 + 1), ... , jN(jN + l)., t,
2 l>{ .-. -
Zxa.Kj, , j \jIj' - ' 1I '
~, ':' . ,., . ,', , .

12\j1j =(1-1++1z+1~)\jIj = (j+P)\jIj =j(jf.l)\jIj' ., 1=1!+12+ +1N

I qIa,
,

z:
;t

2 , 2 /Z ~ }z! +)z2+"'+ }ZN'

j \jIj = j(] +1)n \jIj.
J( J + i),
.
,
:
.
, " v, . v , , J
j :
2

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

J,
2 2
~2
(j ), = j(j + 1) = (j-jJ, + (jz), + (jz), = J i .
.
= I(}-),'(}+)', ++ 2 =+! ++ 2 ,
'

+ ! = ,
: = ! + 2 + ... + N'
.
a~ = j(j + 1) - ':':' 2 = (j + )(j - + 1)
,

TOJfbKO , aiI ,
.. -
. ' ,
72
73
 ...... 2 \ , 'l3qjt!.~
f"q f 1 ',
Q. (Jl',~~;),~Iti811111111
: 1, , , j2' j\, j2 1 , , '.
, , ~ . , , , lVJ'LnllO'"
.

21 + 1. ~ ; '. ]~
J(max)
{2j! + 1)(2j2 +J)I , .
~qG~,
L. (2J + 1)= l + j2)Ul + j2 + 1)-
J(min) li,~r
!, 2' (2j! + 1)(2 + 1) ~ _ J(min)(J (min)- 1)+ \ + j2 - J (min)+ 1). " , !~~1'\1,1(:
~ ~~ ~2 HOB~,
, 'I 1, " (2jl + 1)(2j2 +1), IiQ1B6~#tt
: J(min) = \jl - \ ~I,j9If~
.,""""'! : ,;N- I

' ' 6' 'Ix ml, ' , i/'t~tt~ ,'"

ll' ei (. 7.2). , . , ~!9". '
" + . 7.2, : , xao]J~Wr .
. MQ~HO , " )), j2, J J.&
, 1,
, (21 + 1) , "
(21 + 1) Z. ' (7.141) .
; !. ~ 1
, == j\ + j',
' "~2:, '
".
, : J. ~. 7 .6~ J . " ,
J == jl + j2 - 1 , , ,'. '.1, ''.\
, )J( 1 =j! + j2, 1
J = j! + j2 - 1.
~ * ' 1:
1 , 1t
, l:l, q, , 1 ,
I
2
\,j j/ (i = 1, 2).
7:,~ >j11nJ >j2m2 ():::: -jl' - + 1, ... ,j); ~2 =
rl, mz, : :::: -j2' -j2 + 1, ... , j2)' (2Jl +
+ 1)(2j2 + 1) - >m1>NII2'
m2 .
Jz:
m1,

jl jl + j2 "
1 , !
j\ j2 - 1
)
lz> m1> m2 :::: (}z) + }z2)>jlm;>J2m2 == (}Z)>jJml )>J2m2 + >Jl m1(}z2>Jzmz) ==
jl + j2 - 1 2 :::: ( + 2)> J1m1 >J2m2 .
,,1
jt -1 j2
{> m1 >12"'2} .
-1 -l (2jl + 1)(2 +J)
j2 - 2 +j2- 2 3 "
, J:
jl-2
...
J :::: L.L(j\ j2 ) 2!J )>Jl m lq> m2'
ml mz
75
74
 l j2 l 2 IJ ) : , ,
~2
- . "'- ' l1 I1 S . -
, , :
, ' '
M s = +1, -
=~l, + 1712;, - j~l;s;l-:;, +J2 (. . 7.2): '

81,1(1, 2) = a(1)a(2). (7.16)

7.7. .~ . ~
,
,
~ ): . 81 1(1, 2) 0
(. 7.1). , , S_ = Sl_ + S2-,

, m . ,
,,' " , 1 S_8 I,I(1, 2) = S_a(l)a(2) = + S2_)a (l) (2) ==
(Sl_
, :
ts =1/2 -'-1/2 '~, . = (sl_a(Ia (2) + (1) (S2_a (2 = ~(I)a(2) + a(1)~(2).
s = 1/2, ':; (7.13)
~ . '
(7.14) .!
S 1, -,!
.
() ,'
.
, q>ml q>mz, '
"

81, (1, 2) = .1 [a(I)~(2) + ~(1)a(1);' '" (7.17)

8.1 -1(1, 2) M s =-1
(1)(2) (Ms = +1); ,
a(I)~(2)(Ms= );
(7.17),
- (7.15):
~(I)a(2) (Ms = );
~

~(1)~(2) (Ms = -1). (7.15)" 81, -1 (1, 2) :::: ~(1)~(2).

s S = , 80; 0(1, 2) ,
2,5 , 80,0(1, 2) or 81,0(1, 2):

2,0 1
80,0(1, 2) = .J2 [(1)2) - ~(I)a(I)].
1,5

1,0 . 7.3
.
0,5 (2S + 1)

S; ,
2 3 4 5 Z.
' n1.
S= , .
. 7.1.
ubl. S = 1 (h ) -

76 77
 7, .J/81/2, 1/2,1 =(8-8+ + sz + 8;). ~ [2(l)(2)() - (I) (2)() -
i

s Ms 8 s ,Ms(1,2) _ p(1)a(2)a(3)] = 8- { ~ [2O:(I)a(2)a~~) '- 'a(1)a(2)a(3) -

1
00,0(1, 2) = .J2 [(1)(2) - p(l)a(l)]
_ (l)(2)()] } + ~ ~ [2O:(I)a(2)P(3)-:(1~~ (7)(3) -
+I 01,1(1, 2) = a(l)a(2)
_ p(1)a(2)a(3)] + .!. _1 [2(l)(2)(3) - a(l)p (2)(3) -
- 1 4~
1 01,0(1,2) = .J2 [a(l)p(2) + p(1)a(I)]~
_ (I)(2)(3)] =~ ~ [2(l)(2)(3) - a(l)p (2)(3) -
4,,6
-1 01, -1 (1, 2) = P(1)j3(2)
-(I)(2)(3)] = ~(~ + 1)~ [2(l)(2) (3)-
unu. ,
(7.15). -(I)(2)(3) - (I)(2)(3)],
r<.
S: 3/2 1/2. Ms = 3/2 (!; J/8 1/2, 1/2, 2 = (8-8+ + .sz+8;) ~[(1)(2)()-
meml~le ) .
_ (1),,(2),,(3)] = s { ~ [,,(I)2(3)- "(1)"(2)a(3)! +
6f2, 3{2 =(l)(2)()
+.!. _1 [(I)(2)() - p(1)a(2)a(3)] +
, 83/2,3/2 , 2J2 .
+.!._l [a(1)p(2)a(3) - P(1)ci(2)a(3)] =
83/2,1/2
1
=13 [ (l)a (2) (3) + a(l)p (2)(3) + p(1)a(2)a(3)]. 4.J2;
= ~.!.[(1)(2)() - p(1)a(2)a(3)] =
42
M s = 1/2 (
). , , = .!. (. .!. + 11.!. [a(1)p(2)a(3)- (I)(2)(3)].
212 )2
83/2,1/2 81/2,1/2'
, , ,
: ..

- 1/2
s- .. '
.
1
81/2,1/2,1 =~ [2(l)(2)() - (l)(2) (3) - (1)(2)(3)] (7.18) 81/2, 1/2, 2 = ~ [(1)(2)() - (I)(2)()],

, ~
81/2,1/2,2
1
= .J2 [a(1)p(2)a(3) - (I)(2)(3)], (7.19) ,
~ +1/2:
,

= 3/4:
~2
S , 1/2(1/2 + 1) = 81/2,1/2,2 = .1 [(1)(2) - (I)(2)](3).
79
78
 . 7.2. 1-3 -i
:

0N
s, , k
= (s +1. 1.
2 2
_1.2 .!.\S
2
, ~8, N~i ,1' a(N) +.
) 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+-
2

~N
0 s, , k
=(s-.!.2 1.2 -1.2 .!.,\s 18 N
-i
) s-'2'
1 a(N)+
2 2, k '

S -1. 1. +1 _.!.\s 10 N -t" 1 ~(N) .

+( 2 2 2 2 ) s-"2' +2:' k
1 = 1,2, ... ,jN-n
01/2,1/2,2 = J6 [2a(l)a(2)~(3) - a(I)~(2)a(3) - ~(I)a(2)a(3)]. (k
s-2:

COOTBe'FCTByeT , -
Ms = 3/2

i:>:' ", , .
~(3), +1/2.

+1/2 M s 1/2. =
S -+' '
1 1
2 '2 - '2
1 1\
'2 s )
I = -
S,-ft{ +1
2S + 2 '
,. 01/2; 1/2, 1 I1 (
, 81/2, 1/2, 2 -
" 1 1 1 1\ '1 S + +1
. , 81/2, 1/2, 1
(S +"2 "2 +"2 - '2 s ) = 2S +2
(7.20)
,

(s--lS) " v ;}<

81/2, 1/2, 2,
S
. ,
(. 7.2). S = 1/2
=
(S = , S
N
=
=
1) ,
2. , S
N 3 (l 2),
= 1/2
S =3/2 (s-H M+i -i\S)" ~S;:.
). .
. '~ ,
, - . ~ .

( J2 m21 J, )
7.8. ~OMeOB.
. - ,
1 1
2 -2 --
S+- 1 11
2
'" 2 -S ,,'
)
( =
1, (
N- TOB~e s ~ 1/2). :

K :
] = 1+ s. J :
81
80
 j = 1 1/2. S- (1 = )
j = 1/2.
, :: -~r 1I:.~~:
. ri - , ,,
, Ii I N~> 1 I \) I I I I PoJ3> 1 I \) 1 I P-I~>
' nFf-m ,
so u

3/2 1/2 1/2 -1/2 -1/2 -3/2

Hso ~ ~]; ~ ~(i.s. + i ,s, + i,s,) ~ ~ <i.s- + i_ S.) + i,s, J I Ptfx) 3/2 .!.~
2

~ - KOHCTam<l - , ! I P1P) 1/2

--~
1
2
-~
2
V(r) :; ,
, i
I } 1/2
-~
2
I ) -1/2
J2~
2

~2
1; ~, I _\) -1/2
J2~ 1
--~

2 2
- .,.
. I lP) -3/2
.!.~
- . 2
Hso
( = , 13) (7.12), (7.13) ,

' . l' ii, , Hso

=
-l :
1. : 0\ =(~~]. 02 =(~-;) = (~_01) -
1
S; = 2"0j; -

~~~~~~~~;:~~~~~;~:::~ ;:~~;:V:~~~~~~I~~~~~~~~:;:~::
~2
Q S

2 1+ ,2(, <).
3.. 1+ 1_,
lx l 1= 1.
.2 ,
4 1 1+ .
, , 5: c~ 1/2 , -
(. 7.4). , Hso
, (~)-
: fI ' = + m '
, s , Z
I

6
r< .
- ((S(7.20)),
_ 1/2
: j = 3/2 +O,5~, j = 1/2 :
. ) = ) - , '. ,
-.;.
Ms = 1/2); ) ~ (S .
82
 8 (

.. . ), -
V(r).
. ,
V(r) .
,

, " i , .

: I;I0H!,I j
I
:

, t
' V(/- _/).

. '
. P~.
lj - '2 , '
.'
[1 (
2
- 2 ~ r
2 ) . 1
+ sin Sl
(. ) 1] 2

+ sin <2 =
2
i , ~
- ~J
fI q 112 1 ( 2 )' 12
=- 2 ~ , + 2 2

,
, :

~2

-2
--1 - a'Jf)
( r 2 - . +--+V()\jf=IjI.
1 \jf
2
(8.1)
2 ,
2 2
~2

R= mll1 +2~ 1 lz

l +2 '
' u

: - 2

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

2

, 1 lz m
(. . 7). \jf
=1 +2; = ,/2
l +2 \jI(r, , <) = R(r)Yim(e, <). (8.2)

, ~
-- _ 2 2
- - - 2 + V(r). R(r).

( r.) =() (-)
1, 2 \jI r , - (8.3)
84
85
 (8.2) ~
, ,
. Y(r). Z4
r I,'~
" =- 2n 2 '
, ~

, ~
, ! Z2 e4 m 1 (8.6)
. . . . ' ',~ E/I=-~n2'
V(r) -
(8.3) 1 ,
~ , aToMH~IX -
2
~~(2
~2 dr
dR)_. l(l +l)R + .2 [ + Ze
2 2
]R = ' (84 , O{J == 22 == 0,529177 . : "
r
,
.. i
::, i~
- ; Z - ;
.
; (~)
HOBbJe
4 2
r EO{J 1 .'=-2 =-=27,211 .
=-; ==-2-' Ii
O{J

~ , :
, \
00

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

2 I le , n I. . .. ,
- ' ], ,' 'If(r, , <) ~I9
,:\
. (8.4) : :

'If~l(r, , <) == N"/p1e- ZP / n ';/(2Z j n)l/m(e, <): (8.7)

.l~(p2dR)_I(l + 1) R + 2( + Z)R = . (8.5) (8.7) .
2 dp dp . 2
n == 1, 2, 3: . .
(8.5),'
, . :

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 R
2,0
1
0,10

4 6 , ..
5
.8.1. 1s
)
; n , l - -: . 8.3. 3s (1), 3 (2), 3d (3)

;:. - . <; 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). ; ~ v.
1s 2s: ; tI

r < 2 . .. , r > 2 . . _ ( . , ~
. (, , <)
~ (. 8.3). R (r) - .
2p
~Jra j ;II6 2- 2s-
.
,
r .
<,
1. n. R(r) n = 11 - - 1. .
2. r = s- , dr:
; .
3. r -'t 00 R(r) .
dw(r) = R;/r)r 2dr = Pn~(r)dr.
PnZ(r) = Rn/(r)r.
ls, 2s,2, .s, 3, 3d . 8.4, 8.5.
PnZ<r) -
(
~) ~

' .

. :
2 4. 6 8 10 , . .
12 e-Zr/ n , n
. 8.2. 1s(1), 2s (2), 2 (3) :

88
89
 3 : Is, 2s, s:.;s.
4:
~
0,6
5. (v(r) == --;: )
1 _
2-; 2J /2 .

0,1

5 10 15 , . .

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

"7
2

0,12

0,10

0,08

0,06

0,04

0,02

5 10 15 20 25 , ..

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

, , n
I;l . .

1. 2 _:. ( 2:1)
1- r .

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

90
 9 <1'0,
. ,

, '.
(9.1)
',
(').
,
,
.
,

.
, .;.i (')
. ..;; : (') :
- . .
Il . - () =
, : '
0' (. . , )
(9.1) '. , -
'. .
(
'
) .
v ,
' fI . -

' ,,
'1' ( ),

= (') = f'P* H'Yd't, (9.2)

= ('} J'Y* H\Pd't.=
' ' ~o'P ri
() , :
,
. , = (') - -, , ':
, U (
).
'1' - = J(' + 0'1')* jj (' + o'P)d't -' J'* H'P~~ = J'* H'Pd't +
.
J J J
+! '* H'Pd't + '* Hc'Pd't + 8'* H8'Pd1: - J* H'P.d't ""
";' J'* Ho'Pd1: + J8'* H'Pd1:.

,

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

2 2 2

= f 8J* H'Pd1: + (J 0'1'* H'Pd1:) *
(') ~ . (9.3) '1'*, '1', ip,
, ..:
, '1'*. '
,
. (9.3) ,
, '1' - (. . 1), . .
92
93
 ,
, ~ ,
.
'1'* ~
' , .~ Xi:

1 J J
'(') = o'f'* wd't - o'P*'Pd't = 0'1'* ( - E)'Pd't = .
, }j
(9.4:;

'1' = LCiXi,
i=1
./I 'r* ~
- 1lI: (9.4),9 ,
l j1.
]) f* : : ~

'1
(-- )' = . (9.j)j

, , ;!
. ~ paccMO'FpeH iI.
, : '1' HOBOroi , ,
,
f J
'(') = '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 Sij:

(9.5).
f
Sij = X7X j d't.
l Oll ( ). ~ Q t Q~~
I9 , HeKOTopH~ :
, : ~

'1' = ,-\ + C2e-2,

l, 2 ~(! ; l, 2 ~ .
'1' - .
, . 1'
; (i = 1, 2, ... , ), -
2, l, (2) ,
, 1' 2, l, (2)
: L (Hij - ESij)C j = . (9.6)
j=1

! = , ! = , ! = , ! = .
1 2 1 ,2 :

~ l;>
(Hll -)l + (H 12 -ES12 )C2+ ... +(H1M -ES1M)CM =0,
, , , ;:-,
J!: -' (H21 -S21 )l + (22 -)2+"'+(2 -ES2M )CM =0,
,..!
,
, ~
95
94
 , 'n n.
, i , Xi
,

'n:
( . - ;):
' = ,
'( - ESij)1 = , ', - .
.

oqHOBHoro
(" ( ).
(HI1 :.... ) ('2 - ES'2) (1 -ES1M )
(2 , - (22 - )
I .
ES2,) (2 - S2 ) =. (9.7
, " 2 , ...
( , - ES1 ) (2 - ESM2 ) ( -) ~
,. : :::;
6, ! :::; Erar , ~:::; '5. , ... ,
(9.7) . ~ ,
. (9.7), - ~
,
, ; (" ... , ). j (
I : ~ (9.6), yj
) .
{}, fj: IJI

1 'J

d: HOPMflpOBIO,I

, i :
'I = L..CilXi' .
i=1
'
(9.6) . .. (
; '
. )
'I:
,

' .
L.. L.. Ci~SijCjI = 1.
i=l j=l
.. i ~

,
.
.
, r
n

(
'n =L..CinXi' 90).
i=l
~ -
JI : ' . ..' . .
~ . i1-
, ,

;:~].
Cl1 C12 , 1 2

= [ ~~: ~~~ ... ,

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

96 4 rt 97
 , . 1 2 . 1
. . : [ + c~= 1 r, 1 = 2 = J2'
~ I:2 = H I1 - 12 .

[~;~ i~J ' (9.8) ,

(Hi1 - H I1 + I2 )l + 122 =
Ie ; EI,

. , , :J
{') 21 = 12 . . (9.6)
,
1. 1
(11 ~ )1 + 12 2
{ 12 ! + (22 - )2
= ,
= .
(9.8~, , ! == -2; ! = .fi; 2 =- .fi'
i '1 ''I{~Q:
1 , r"(':

'. . '1"" '. . 1

'(HI1 - ) 12 I f'Pi'P 2d't =''2} (1'+ 2)*(l -X2)d't = '2(f xiXtd't-
I1 2 (22 -)
-fXtX2d't + f X~x;dt- JX~X2d't).'; .!. (1- + -1) = .
,
.. .... ' ,2
1,',' " ,

i .r 'l':: ~ , .,
(HI1 - )(22 :- ) - (I2 )2 = .: ' 1 'F 2 " ro.;[::
,ff" l :',

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

.

, 2

1, 2 == H lI +H
2
22 + (H I1 +22
2 J' -11 22 '.+ 212--
, . 2'

:::: 1I +22
.'
11
2' ,
(H -H22
2
I1
J+?2' (9.9)1
,~
,
f t 2 , -
q , Hll.~ 22 , ~
~ : . .
J
1 ; 2 = H I1 12
J
riat~, -1 . ,
~iJ: coorBeTcTByeT 1 = HI1 + 12 ~ -
: .... . , . , " .
J1 J,30 (9.8), -!l

.' (1 '1- 11 "-' 12 )1 + 122 :t:

.

1 = 2'

98 99
 l:i
(~ , I ,
H lI ---< H lI - - - { ):

-10
-4
-6
J.

-6 -14 "
.~ . 9.1. : ,
- H ll = 22 ; - H Il ; 22 ~i-r ,
. 9.1 (. 9.2) .. ,;,\. ,"
m , ro, P'I:lc. 9.. 3 m
. ! 2 ' , , . .
, , I~~l?. (
() , , ~i~, Xi ).
, . (-24,11) l' . 9.1.
. 9.1, . . 9.4ridir:
. ! I:i '1'2
H l1 22 '1'2'
, ! Xz l (;~~ uz II c~.
, ! 2 - , ~.. (;:-9,5~4). :;()l;[ (IO
. . 9.1.
!2 ,
. !2 , , ; .
, r: lJ
. : (
, H l1 i:- 22 )
, ., .
( (9.9); . 9.1, ).
.
IJ, ; .

. 9.1, , IQ -;
.

. -5

-10
, 9.1
' -15

/N n ! 2
-20
0/1 -24,114 0,867 0,195 0,458

0/2 -9,554 -0,477 0,594 0,649 -25

0/ -5,331 0,146 0,781 -0,608 . 9.2. ~

100 101
 9.2

"
-12
. l "
2

:
'\ -19,385 0,828 0,561
' 2 -8,615 0,561 ,
-,828

:
'\ -9,010 0,984 0,050
' 2 -11,463 0,360 -1,047

-16 -5 )
[ -5 -12
l '

. 9.3. I !
( l, 2) ( S12 = 0,3).
, )1
. 9.2.
;; ,
(. (9.6. ! ,

:. ,
: :'1
, .
= 1. ll + 22 - 2H12 S12+ 11 + 22 - 2H12 S 12 ,1 .

1, 2 2" 1- S?2 - 2(1- S?2) . .

. -~, ,
ll 22 12
- 2 + 2'
Cj.,
(1- S12) (1- S12) . -,
,
-15,8 . "' "
.. 8 m ' . ,
-16,0 ls R 1s(r) =
= 2- ( ).
-16,2
( . ) -1/2.
-16,4 ls

-16,6

. 9.4.
-0,50 -0,48 -0,46 -0,44 -0-12
~
i
~ - , ; N - -
( l) .

102 103
 ( ) () , 9
, , .
2

~ 1 ('2) R(a,r)= Ne- ar2 ,

=--- r - +'1-2- -1 .
, 2 1 2r r.
" 2 ' (9.10)'
, : / .., :
ls(1 = ) , ,' ~
Q Il ,
-f2n;...22dx
= 1 3, 5... (2n -1) "I/n (r > , n = 1, 2, ... ) ,
2n +! r 2n+!

= _!j R(~, r)~~(r2 R(~, r) ]r 2dr-

-f, -

r2x2 dx = -1
2'
2r
2 2
r
-l' ,
- f ":"R2(~, r)r 2dr = :
r

( r 2 R(~",r]"
=--21 [-fR(~, r)-

.dr+2fR2(~, r)rdr.

] (9.10). N2 = 82 / , 3 2

- 3 (2
! E=2a-2~--;-.
.. .. (i) = 8/(9n)
f (~, r)r 2dr = N2 f - 2 d = 1.

'
(mi) = -~ = -0,424 ..
.. ., 3n

f xne"'axdx; = ~. .

,

n+l (9; 11?, ,
0,076.<:(. = 2,013 ,
- 13,6 . ~, r)
= 2~, n = 2, 1/(4~3Y~ , r) (. 9.5) , -
, ~ N = 2~3/2. ~
R
l1
paBeHcI~y (9.19), -,
2,0
, q
, (9.11),

=!(~2
2 - 2~) .

~
, ~, -
4 " ..
: ~(min) = 1, (i) = -1/2 (. .).
, '::l ". 9.5. ls ( )
, . , (, )

104 105
 (9.13) (9.12), '
, wf ",
> 1. ~
'1

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

lI. G~~ :f.:r . =(E~O) + ~l) + 2E~2) + ...)('P~o) + 'P~l) + i 2'P~2) + ...).
;:r : ~
:~
,

, coJ,

c~eHHe ( ~ (9.14)
W - . '. j
, , le ~ (9.15)
I9 , , !
r *. ~'i 'P~2) + W'P~l) = E~O)'P~2) + E~l)'P~l) + E~2)'P~O) . . (9.16)
W ,
. , . (9.14), (9.15). lI
~ .
, ',
(9.15) . ,, , -
; : 'i E~O) . YMHO~M Yl' ('P~O*
JI .. ~, ';\1'0 ~J?,qIf ~J?
o'P~O) = E~O)'P~o).1
, - l' \

,:
, BBO~T HaJ
, - , !
, () ~
. , ;] 'P~O)
~
j
"1
.. ~ :'~),
' n = n' n , (9.1i~!,j
. . E~l) = f ('P~O*W'P~O)d't= Wnn

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

(9I.U
' n = 'P~O) + 'P~l) + 2'~2) + .. . !
.
, ) 'P~)
. ,' :
:

J'P:'P~O)d't = 1;
'n , k = n
. , 'P~I), . 'P~I)
'P~2), .... ~o). .
107
106
 . (\{'~O* ,
t<: Jj .'d:
, , :tR
ir .


: i
. , .. '

' ! Ir ,'~, ~..

Win+cf') E/~) :;= cf') E~O). ! " " ,,1

, \{'i~) = L Ckm \{'~2)

k=1

(1) _ ; Win (9.21)~ ri -

/ - () _ () ,
:
' ',:. ,

n /

.
,

\{'j~) -
n -~'E(O)
n + Wnn,
.
\{' = \{'() + ~, w'n \{'() (9.17~
n n .... (). () k' !
/ . - / ~ )
... (w"k - ; Onk )Ckm ,
k=1
(9.17) iC
. , J
, :
:
f (\{'~~.* (;() - 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) E(I) E(l)
f
U
nl' n2"'" n!' . .
E~O). ,
:
( ).

. . wr
-
: < \ " , ,

!- : E~O), 1.

() () () .... .1
\{'I , \{'2 , ... , \{'! ( : n). 7 , V(x) = .

108 109
 2. , \
CI<OM , \: ,IP .
\, 10
'\ _>' " _
. ,~., .

3. , TP~Te~o
. . ' "
'. 4. ,~~~t
, n + dx 4
5. .
B~
- n = 2.
6. ~ , !., . -
, I< t
f '... I ' ,

ls. '
7. '
. -
. ' ",!, " ~ ".

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] =

k 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. (10.2)

k dt. k , .

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

?J' am(t):

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

= _.!.- I, ak(t)Wmk (t)eiIJJmk / , (10.3)
/i k

Wmk(t) ~ ~; k =
= ( - Ek)!/i

111
 !
l (10.3) ~( .
, ~ -
a~)('t) ( ),
.; .( , , I
i ~ , -
, ~ l
, ( ag)(1). ()
(~ri,
i ~ k, ~ k ~ ;
). ,
k + a(l)
ak = () k + (2)
k + ... , , Wmi(t) .
. , ,
1 (10.3) :

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

da(O)
_k_, =0 'i(' t) ,
dt ' k;f:. i .
,
da(r+l) . t = : W(t) = t <.
_k_ =
dt
_!..1i I.a(r)W:

k(t)eiO>mk t

(10.4) ak(t)
. QI k:#: i, /ak(t)/2
, , , J!. '
Ei , ( 1) ft (
\Pix, (), . . ak(t = ) = 0ki' /ak{t = 00)/2)
m) : (, , j>~ ljeKOTOpble ,
i: ,
, , ,
da~)(t) = _!..W: .(t)eiO>mi t . , l:lI ).
dt 1i /
, /am(t = 00/)/2 (Pim )
i m.
( :#: i)
, , -

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

Wmj (t)eiOOm;f dt = - *J
Wmj (t)ejooit dt. (10.5)
.

a~)
(10.4):

;;)
t = -
i . (-i t-
h Wmi (t)e/ OOmit + t; )2 . l
t ,
W mk (t)e/ OJkt W ki (t')eiOJkit' dt'.
. Bo~ , !l
,

< t < 't,

, - 0 0 +00. -, :-
m ( :#: i): :

112 113
 . , t1 t
= i == ( - /., ,.: 3
?! :, ~
' . ."
' . ' 5'" . . .~
~pe:~~ i~~;,t)'~~rY _.~~. BpeMeIi~
v .

< 't ~Y~ - -const, . ,

Yi?1i~ (10.5) t> 't
. ' ~ r I

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

, ', l - Ei
,:~ pa~Ha

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

l1:- _
V;Z st 2 ( .'t/.2)
l,
10
I:1E "
. ). , ( - -(Ei- ,)2 /2 . (lo.:j
. 10.1. f( - ) '
. iI
( :, ' "'1
::: /2 ( (~mi"': 0))/2), II~. 'ylI
W(t) = VO(x)cos( t) = VO(x)( e im! +e-imt )/2. . 10..1. ,J(I~Qcr
, , ?lJ;~,!< fI~r.: ~Q,r (
) Ci' ,~Jj't BpeM:eHe~.

"

.

. ".
(10.:8)'61' ' ,,'
' 1 :'" ..... , j' . "
-
iVO 't . . '1, '.Imf : .Ji: I1:,. ( ~ 0.:
... ; ,
..
(lm (1:)
'2
=- - J'ro" ( + e- )dt =
,.
'. , "
- -vo- [ei(.mmi+ro>t -'. 1,
- ..... .. lJ'
. + e,(romi-m)f_ li~:[Sin(Xt)]2 = lim[xt L(xt?/6+ .. :]2 = 1.
'. 2,' (mi + 0) '. ( , - ) ,. xt -;0 xt xf -;0 'xt

:(~~~~ ~ Il ,
. , ' JiQ 2 t 2 (..
( ~ . JiQ), .,.
). 1:Q (10..7) ~ . . ,
,
;r ~' BpeMeHHbIX ~,
. '. .
,
2
Pmi = 2Vo {l- cos [(romi - )1:]) = Vo2 sin 2 [(i - )1: /2] .
. '
(i _,?J)2 (~, - )2 /2 (10..81 : ~

I\CiK ,, . bePO-1
, , , :,

' n ' . , . 10..1.

, BJIaB .
,
2 JiQ 2t 2 ,
sin (xt) _( in(xt)]2
t-------
s.

-

2
tx' r (i"'- ),
.. ( m)t/2 == !if 1t =
114
115
 = 2r./t. , 2r. Vo~J 102 :
:~ dN m + dE p(Em)dE
, , 1
t ' :

; ,.,~,,' \<~i:~ ~ , .
'niilQ:~J' ~
" .":~;' ' , +00,
----'..L-_ ;
, . . "~ ,{ , "
-j ..~. ',' '"" (10.9) :

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

. . .'.'
) =1iVo n( ) _ [(; _)/2]2 l
,<l., -1
- 01 2 -~J sin 2 [(comi - co)t /2] dco '.
2
. =1iVo pn(Em)t _ [(co i - co)t/2]2 1
~j\1 ~ m
. , ,
, d = (; - co)t/2,
, d '
,If E~: :
~ ,
,
.
,
.


, ' . 6
+ dEm ' (10.10)
Ii-4 = 2r.n Vo2 pn (Bm).
, . dN = p(Em)dE~, '
, C~OPOCT , ,
() ,- (. 10.2). 1l
.,'
. (10.10) m~
l
.
.
P(t) = "\' . (t) ==
k.J
f,4J/~? sin(2 [(; -)2co)t /2] n ( )dE' ~ ,
' ; - .

m r:I, , (10.10) - ~
" ,
<). d ; ','
. '
<i () . : <l -
, ' ; ( 10.6):
() ,
_ l
, 1
= (; ~
- ); -oq'
117
116

, m ::::' ; -
. ,..
/( - E ) = sin [( -E;)t/(2h)] = Pmi(t)
2
.
i m il.
( - ; )2 t /2 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).

1 000
, ( ) (1 = 10-9 =10-7 = 10 ) 100
(; ). ,
(10.11~ I! , . Q ~9I
, ,rJ~ !>!
(10.8) (10.11), 1 (100-101 ). II' , ~,Q
( u '-, ().~ , ,"L'rO ~
state-to-state);' ' ; 2n / ~rr
. n," I

2nV;2
i~m ( - ;). (10.12)~
t) == -? cos(rot).
:= - ; ;
W(r,
! ,;
J:
, , , ~, ( 10.12) rJI:
, ( ) = ()' (10.10) ' Vm;,
Wmi : ,(
(10.15)
, 2n 2
Wi~m =j}IVm;1 ( - ;). !II
(10.13)[1 ,
~
.
,
. t Q~ -. (10.15)
: : EY~ , ' , '; -
(10.12) ( - ; ): ;i
,
.
2n, 12
;~ = 1; Vm; ( - ; ). , I~
(10.14)9
, . .
.

> ; (~ ,
.
=; + ), ,j
-

118 1
'1 119
,.. . . :. . ~; 11
~. Vmi ','
~ , ~

ro (10..15), -1
.~ .I . . ( ~~.'
- ,.fi) -:
.~. , 1;l!
() < , :4 11.1.
. .
oepa'CU

- ,
, . . ,
1. W = V(I- e-k/). j
.
q,1 ( ).
. 1
- () ,
2. " Z,
. ( ) OCHOBl ,
. MOMeH~ ( ,
t '
2pz? " ). .
'' , o~
3. = (1- e- kI )';

',' . - 'I:
(t > ) . (), , n: -
e-k(f-T) .
u

. "
Is-
2pz T(k(t - ) 1)
, '1!r '.
'!J n-t> ,
4. t = /2
. 06.' 130 , ~60/n
. 2pz . ?
. 3600 : ~
. , -
5.
2
J(x) = sin (xt / 2) tl , -
2 , - ,
( = -10,0, +10,0; t =
6 .
, 1, 2, 3). - , -
q, ~ - .'
u . ' ,

.. ' ,
I , ri'. IJ :".
11 . z
. '
7.

-10
[ -J7
-.J7J
-4

. 11.1. Otp : 11.2.

121
 ~ ,
; ~ ~ ~ ~Q. .
(. 11.1). ~ << , '
( Ka~ . ,.
) ~
, , Z ~ -, -, -z ( . .11.2). . '!I
~ !f~ !~ . " . ',~.,' '
, ~ , '
. 1 . ~
- . -:: , - . , I, -
~ ,')) , ~ 1, . .
. BeKj : ;
. : TOlieK .. . ' , :;,'I::
. 'lJ'\,
- 1 , , - 1/.
11.2. ~ .
. ., '
,;';nn G~~I Q~ ( ~~ ; Q:
) , (~ . .R; " G. 1;' t
B~ ). ~1 n - r(R;) , '
, , , ... ,, h" " ~,~ . ,~)jll
n/( . . ,d 1:. , ( ::
1. n. ( /(n, /( u).~ G. n , Q,,:"
, :"i r(R;),
. : py~,.,j . n .
: = . ' " . r(R;) /( x(R;!
( 7" ), . ~ R; .
) f ~1 ' /(1 nm..u'
r.r.. .. '' . , .
2. .. ~~ , .,. ,
: ABCDF = A(BC)DF = ( CD)F = A(BCD)F ... !~~ r(R;) . ~
-'! . ,
( ).'~ .
3. (), j .
: = = , -' ; .. n ,
. 1~o n.
4. A-l, -.; . n! ., n
, : -l =A-IA = .! /(. ,:
, G :: -
(l) , -I , () .
G. G ' . .
, , '
. G F :
=
1 2
..
3 ...
'
n)
.. '
, ' . ( 11' 12 13 ln
' . , i - ,
= , ' ' = .
k
k. .
123
122
 :2 1 I4i;' 11.1
:
I.'p' CZv
- 2'
, ~ 2 (Jx< (Jy<
. n ~
1 n ' " 2 0::;:, , ' (JyZ

. 2 2 (Jyz' , (Jiz

, haccy,. .<J , ' 2

(Jxz (Jxz (JyZ
.~
(JyZ (Jxz (JyZ 2
-'l= .
, p~ C2v h = 4. v
n6 .
'. '. .
:., " , (JYZ C2 ,
' '', 180, ...:-. [
, yz. ,
. , ,
(, ~ .. l,'I ',.
), , ,
; CH 2C1 2:
(, , " " -
(Ji ).
, ,.
, , -
(Jxz. , (JyZ C2 = (Jxz.
11.3. .u 'h , ,

QJi , -
. , ] . II
, .. 1 (. 11.1).
'. of: ~ . 11.1 ,
: , tv
~ eTc , , -
. . , . . 11.1
'~j :
(. 11.3): 2-o~ 1)
, J ,
1 ---' 2 ; ~, (
- xz ( ",! );
) yz. j 2) ..,..,.. -
, ~ ; .
, - 180fi 3) t;~ ~,
( 2 ) -; ;
xz (Jxz) YZ (Jyz). ': 4) .
(1 , , . 11.1
. 11.3. - - ) (. .. j ,
) : Hy C2v' ~ -

124 125
 . 11.4. rm~ C~v ( -
r(R j )
..,!<<1 1,2-6' ). , '
,[( )],re (m ";" : .:.
C2v) , .6 ( ), -
. , , ,
.6 , C2v ,
(R. 'F
(R :
-
. ': )
(R
'" . . ,
(11.1) : :

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

C2v' ,
.\:" , - [PdC12Br2J2- .; . 11.4j : 1800 . l!JQ:
,:I>~ IO ~ 5: " 9 Q. I):aK
i1 Q)i <,2) , -
Sl .: " .....
1 1
1 , 1
1 , (j 1 1 :
() 1 (2 ) =
1
. 1 2 3 '',.
1 1 .' '('

"0' .1 0.' :3 = :,2" . .:
1 . 1
5,
' '

, 1 4 ,",' 1.li'
1 ' 0'0 1
"
1 5 (, \,~
,

4 \ /!

1 1 ~' i .: !

J'(crXy ) = . 1 , " , J(cryz ) == .0 1 .0 (11:1 , ( 2 ) .6~ i :t

C2v . :k: ',
1 1
-
( crxJ ( cryz ) ,
l' 1 xz z~, (), ( 2 ),
(crxJ , f(O'yz) , ;. ,
: , .

, 91 ::Jl r , -
:. .,
, ; . ~ I

- ! Mii
i~
; .' ,:q
~ "':"" (); . .. .!I~
() ~. [~ ~}1

.'
, MaTpflll 1 (2 ) =' -1
, .. ('~~
). . :~
, ~

() ~(~
~]

~ (), (2 ), f(cr xz )' f(cr yz ) ~.
11.1 C2v' , "i(
-1 f(cryz ) = ~ 1
2vo ', 1.
126 127
 . , e~ j
, - s~ 2- :
, :

1 Jj

2 2

[~ ~}

Jj 1
() :::: 1 ( ) ::::
C2v ~ ;4 2 2
J 1
11.4.. .

J .j3

2 2

~l~
, II' i '
: ( - ), ' :J 1
f(Cl) :::: ; ("I) -1 (11.2)
1200 ( ), F! 2400 ' 2 2

(Cj) , ''1 "

, ()
~,' .
(0"1' 0"2, ") (. . 11.5).
v .
~ Jj
-'.! ~
. 11.2. : -~
2 ,2 ,2 2
, '
IM . , ) (0"2) ::::
:J
-~
1
(").
43 1

1200, 1200 ,! 2 2 2 2
, , ' ,~ 1 1
2400. ~aJfM ,, . Cj ~
I . v .-;1
: a:J:'0MoB :I~
,, ,' fv ,' ,:1,j
, m r C2v MO~ , 2pz
. ,j , 2 2
, 11,41
. . ~ .

r
u u ;i!
~! f(R) (11.2) v
; ,
0"1 0"2 "
; .
2
0"1 0"2 " "i' ,
} " 0"1 0"2
,
,~
. ,
,
2
Cl 0"2 0"1 ~
; . (11.2) ~
0"1 0"1 0"2 " ; 2- . ,
,1
0"2 0"2 0" 0"1 ; ;,
2-
3- .
" " 2
~I
0"1 0"2
(2 3)!I; -
.'~
128 5 129
 rp 6 , -f!!1 , {.2)
. , ( ) .~ (1l.3},. (11.4) ..
(11.3). '1,f;{1'lA}
: 2/2.,. ':r ,:~
1 .J3
( 'I:I;)
2 2 . 1:, (11.2) i iLUbl,
,..J3; (11.3) (11.4) - ntu/;rrtJUlI , ,' .
1
, ~ v
2' 2
1 ";<',1,.
( ) =
1 .J3 () = (1); ( ) = (1); ( Cj) = (1);:

2 2
( = (-1); (2) = .(-1); (cr) = (-1) . (11.5)

.J3 1

2 2 1s- 2S-0 :Q:wrx
1 , ()~.t;I1~q~i~;~
'~ II~ (:7v ;!>IJ;3:~
, 9 Ix ~~'I'~.(l1})~ 6t.~
, 3d- ~ ~~ 2p z. Ta~~ Q~q~".II;u;~.1.s,.2~, 2pz
, KOTop~e, , ~ qI~t!9~1'1;I~ J~e4>1 f(~ I;l1i~:~ 0;6-
(11.2). , , HeKOTOPO\~ , . . 'rIJ:~ (rr;. ~J1PCTO. ,:) ,;
, .!, ,
(11.2) - . l ; (11.4).,
: o~ f(R) , (11.3)., :..
22, , [ oHi 2 11 2, 6
2 2, 1 1 (1)~ 3dxz , 3dyz , (
FJur, 2pz' ~ ). , :'
: . j: ':
, 2 3dxz ,;JO '
. , 2 3dyz '-~)
(11.3). ;':

() =(~ ,'
. ,
(
).

; " 'r:t",'
.
:.
t :
' - . (11.3).
j ','. (11). ::s-
. '. ', :'
() = (1); ); = (1); ( Cj) = (1); , . . , (.1)
3. v
( :::; (1); (2) = (1); (cr) =(1). (11A~ 1 2, (11.1) -

130 131
 11.3
. ,
(11.1) 1J :
, eJ: l1 'v
C3v,'~ (;
, }
). ., " ,: (11, (12, (1

' : ,
. , , , 1 1 1
, .. 1 1 -1
.~ ~). :II
1 2
2 -1
1
3

(11.~ ( )
, - .

XCRi ), (,(R' - I H~ .
6 . Tc Is- , SI, S2> S. .11.3
' . ]j
ix 'fip . , 3 '
; (11.8)
nu, ' JIiI :
: .
1 ',,' ',:,:, : i
(1) = -
(3 1 + 1 . + 1 + 1 1 '+ 1'1 + 1 1) = 1,
E}k =m I;r}k(R)R (i, k =1, ;.. , )' '1
h R ' ,
(11.7~ 1 6 . '. . " . '
. . '1
(2) = 6.(3.1 +1 + 1 + 1(~n+ 1 (-1) + 1 (-1 = ,
q ,\1I , ~ l ' '
: , . ~ () = -(32+0 (-1)+ 1 (-1)+ 01+ 01 + 01) = 1.
l1.,~ ", 6
I-j: , )i SI'
. G, I H~ ,
~ ,. '_ ' f :
"" ...... -2 ,.., .

(11.8~
,..

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

Q1 fll(R) 1,

~
1 1
. - , ,- , Tpex~ Efisl =6(1'SI +1,s2 +1s +1,sl +1s +1s2) =3'(SI +S2 +s).
. - t. . TO~
, .: 1, 2 ... ( 1 ' 2 ). f,l , . ls-
, o~ ,
g, - (t1g, (2)' ~

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

132 133
 aJI ~ , (11.9)
.' (11.7) : Ma~ (),
rll(R) (11.3), 1' _1
, ;;, --:.
' \ I:l' :
: . , ' ."
~ (11.8) ,::;
. SI:'

... 2
a S1 =~
h
LX a (R)Rs
1 = -(2 SI -1 S2 -1 S +
3
~1: R
. 2' ,
+0'SI+0'S+'S2)=-:(2'SI-S2-S)' "(11.10)
',~'
.'
, '2(0 ",. +-"-'
21 S1 = -6
"
J: ':5'1
,2
,J' , ' ' , ," Jj .j3):J3
S2- - " S3 + '$1 ' - ' _ . S +_. S2 =-' (S2 -S,3
2 .., 2 2 3 '/
~' . 3 , .
'i ". ,,\ . , "
(11.9). ' KoMrioHeH~
u ,
,
: : - , S2: '1 , '

1 ' . 1 (iiI
<( ) = .J6 (2s1 - S2 - s);.<( ) =.j2(S2 - 8). (11,~

, B~ : (11.11)
, , ., ., Ib, (l1.~,,'" : . .

, , 1200 '
~~ .F>"
"

C;SI == S2,C;S2 = S, C;S3 = SI, . (11.10) (l1.1.1),t

: . (11,3). : )!lw
' aSl + ~S2 '+ "(S','
-- 1 m d ( (11;10): ',
<( ) = .J6 (2s2 -S3 -SI)= <'( ),
;<( ) = .1 (S3 - SI) '= <'( ).
, 1( + ~S2 + "(S)(SI + + s)dv = , , S2

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

1 i.

~ ? ? ' , , . 1S-0,
<( ) <( ) : , , = , ~ = 1, "( = -1.

1 :
, <( ) = .j2 (S2 - S3) - , ~ -

~ .

,~ , J<i:l -
!l. '. ' :
1.
.
2;
.

134 135
 11.5. -
11.6.

", o~ fl(~ (3)

,, , .
(3) : (123) (
ro lIpor " ), (231), (12), (213), (132), (321). Il
. , ,
, . 7. ~2

(1)(2)(3) - S ,
f~7(R)ih!k(R)dR
3 5 3
, S(S + 1) = 2 "2 Ms = 2'

-
. , '
" 1
~'1'
. , M s = 2:

, 'i 'k 1
,
93/2,1/2 = 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 1 " ,
, ,:! H~ 91/2,1/2,1 = J6 [2a(1)a(2)~(3) - (1)(2)() -l)(2)()],,
; ! ,
~i ' 1 ' " "
, . . 91/2,1/2,2 = ..fi [(1)(2)() - B(1)a(2)a(3)].
: ,
l 91 92
l
. P(231) 91:
. ~
~ i1: '
P(231) ~[2a(1)a(2)P(3) - (1)(2)(3) - p(1)a(2)a(3)] =
W;,k =f~7(R)~\fk(R)dR. (11.12)1
)~
-j = ~[2(2)()(1) - (2)~()(1) - ~(2)a(3)a(1)] =
(11.12) ' ~,
"

,' -1
\f i ' k , KOTOPOM~
= ~ [2(1)(2)() - a(1)p(2)a(3) - (1)(2)(3)] +
-. ~~
, , ";'
+ .1 [a(1)~(2)a(3) - (1)(2)()].
..(j

137
136
 ' ~ .
(
)(~ . 12). :
=-! =_J .. (231)8 1 =-161 - .J3 62. j (~1) ,
2' 2 ' , " 2 2 ~
. : (<1>;)
, ~, 1.J3 j '~I]?
62' (231)6 2 = - 61 - - 62 ::~
2 2 r (), (\jf;) --:- i': (), ,1?,I

tij(P) = (-1)j;().
J]
2
1
.
,
2 ! ,

, 61 62, ~
1
= -L<I>k\jfk
( Cj), , o~ .jJk
~
v ( (11.3). , iJ . ,
240 aMM~ :
(. 11.5) (123) ~ (231).,~
1t(3) 0J
61 62, , ~
, ~
v J
1t(3) ~
(11.3) ~ . ~
: ij
'h ;
1t(h). .
. fI~

,. J]
, ;
;
l, ~
- <1>; - , \jfj -
~ . : ,
1J ,: '
N-: , ,
~

~
1t(N). .
. 11.5. - ~
, ~

. ~

138 139


11.
1. , Ta~
J;I. ypo~
' .
2 ? '
2. , ,';
Z. . 12
3. , -l f(A)-I. 1
4. 2 ~ IIJ
-< . 11.4.

11.4
,~ . 2 12.1.
,

v'
,'!
v'
i,
1 N , 13 'aTOMHb'IX
+1 +1 +1 +1
, . ,:, '
2 +1 +1
-1 -1
1 5 ): ,
+1 -1 +1 -1 I1 .
2 +1 -1 ':'
-1 +1
, , .'
l kh
, . :if.
R ................ C2z a~ , ' ( )'
a YZ
v
X(R) ......... +7 +1 ' +5 , ' ; ,
+3
' : ':'
, . ""
.rvrn
, J;l
.
.
N-
'(1, 2, ... , N).
- JI ( ). -.
, (
) ,
. -
.
1:
i ,
j, j' - ,
i, . .
: ,
i

141
 12, J, , -' (, . 2).
, , ' ,n :
;~.)::I:I .
, (:)':
'
:'l;t -
. , :"
Ix '~:.
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-
:; "[ " . . . . . : '.
.," -',
( , JI I')
tm:Jm, T.~. -'
-'1'. N~F{~
(}f) ~. . .,~
, ~,i!(~'
nm , : . . ...",;
, -
, . Ji-;,~,
-:
, ';~
-; Jl'l. , "::! I
()1'.: ,};
'(1, 2, ... , N) =det!'1'!, 'JI.2. '1' .... ,'I'NI.=.
, - - .;'
\ : I

, -:-~ '1'1 (1) i\j!1 (2)'1'1 (N)

( ),.,; 1 '1'2(1) '1'2(2) . '1'2(N)
, } , ,.(12.2)
\ = i.
Ji, r , Q ,:
(Q ) -:- n-m. '1' N (1) '1' N(2) '. '1' N (N) i,

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

: <P~(Xi' Yi'Z;), .: 1j.JNi. - J;I,
, , Xms: . . N!
-6?~ , ~IO Q N ~
~12.l) ". , , -

, , : . , .
, , ' ,

,'" ," ,

' ,
"

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

m'
um.u,' ~
-- '/(m. ,' ~, 5I ,
, : " ~ ~
, : (, , h: ):
; ffmfl.
I;l () ,
.0,-\ (-) . '1'1 (2)
~ 1 '1'2(2)
. I2'(I, 2, ... , N) == JNi. ....
. Q~ - .
-, '1'N('2)

142 143
 , r, ,r r ; , 0/.
, , ,' , ..
: ., r
, 11 0/,
: fl, (12:) .
, CTPOi 0/
. , - , .. Q"~~
; .
. ': ,', ,
(JJ ) " , -
. .I1f1 J;30 ; .
, ,J , (
, , . Jl ;
. ,
l .
-. i1 .
:
.
.
~ 1 ~
=-I,(-1)Q . . fI
.fiii. - 1s2. - 0/1 = 1sa"
0/2 = 1s~, 1s ...,... . ,

<U;I
; q- ,
(),
. , 1 10/1 (1) '1'1 (2)1 1 11S(1)a,(l) ls (2)a.(2)1.
;
'(l, 2) = detlo/ I 0/21 = .fi 0/2(1) '1'2(2) = .fi 1s(1)P(l) 1s(2)~(2)
0/1(1)0/2(2) ... o/N(N)
,
(12.2).
,
, Q
,
'(l, 2) = .1 [ls(1)a,(1)1s(2)~(2) -1s(l)~(1)1s(2)a,(2)] =

.: , OCItOBHOM 1
. fO
=1s(1)1s(2) .fi [a(1)p(2) .,.. l),(2)],
::t;, .
t,
.fi[,(1)(2)- (1),(2)] -
; l,\1 .
.
Q -
. 1s(1)1s(2) (
),
.

.
'(/I, 0/2' /, ... , o/KN) ~ , 1 l'e ;J .
N - o/l, /, /, ... , o/KN, , - 1s12s l -

144 145
 , 'l'1 = lsa, 'l'2 = 2sp. rct1 - :
. I
'P(S= 1, M s !::: ) == .1(~l +'' 2 ) =,
' (1 2) = d~tl I=' ~.')'l'.) (1)
'l'1(2) = ~)IS(I)<X(I) ls.(2)a(2). ~
1, . , 'l'1 'l'2 .' ."fi 0/2(1) 'l'2(2) .fi 2s(1)P(1) 2s(2)P(2)'~ 1 ' 1
=- [ls(I)2s(2) - 2s(I)ls(2)] ~ [(I)(2) + (1)< (2)] .
, .fi ,,2, ,
m
. ii" , ,
' I(1~ 2) = Ji [~S(I)~(l)2s(2)P (2) - 2s(I)P (1)ls(2)a(2)]. S =1,' Ms =+1
S = 1, Ms = -1. ,
tr~ ~ :
mi )
; , ~ 1 11S (I)a(l) Is(2)<X(2) 1
'. ",2' . '.' '1 ' .' . "~ 'P(S = 1, M s =+1) = det 1'l'2 \11/ = .fi 2s(l)a(1) 2s(2)a(2~ =
S . li ~ ~
, t) , ' I (1,
., - 'l'
2;
= IsP, \114 = 2sq = ~ [ls(I)2s(2) -2s(I)1s(2)]a(l)a(2);
.fi .
'., '. 1 !IS(I)P(1) Is(2)P (2) 1_
' 2 (1, 2) =dtl\ll \114/ = 'P(S = I,Ms = -1) det I'l'l 'l'41= .fi 2s(1)P(I) 2S(2)P(2~-
=
1
=.fi \114 (1)
.1'l'(1) 'l'(2)1
'l'4 (2) =
1 11S (I)P(1)
.fi 2s(1)a(l)
ls(2)P(2)
2s(2)a(2) =
I ~, ..1 [ls(I)2s(2) - 2s(I)1s(2)]P (I) (2).

1 . .,.
= ~ [ls(I)P(I)2s(2)a(2) - 2s(I)<X(I)ls(2)P (2)]. -
,,2 "

'P1(l, 2)
' 2 (1, 2),
.1 [ls(I)2s(2) - 2s(I)ls(2)],

. (
1 1 1 ), ,
.fi (' 1 '2) = .fi [ls(1)2s(2) + 2s(1)ls(2)] ~ [(I) (2) (l)aj2)] . I
~ .
2 2, . ' . ,,).,
~
, ,
. , .: - .

I(). ()":' .
~2 '. ,

S , i:I ~
- 2s 2 ,
Z.
' :I1 ' m :
. , . ., . -
( Is 2): -
"
'P(S =O,A(s
. 1
=,0) = .fi (' 1 -
"f:'
' 2 ) = ''l, 2)= '1 [2s(l)a(1)2s(2)P(2) - 2s(1)P(I)2s(2)a(2)] =
= ~ [ls(I)2s(2) + 2s(I)I:5(2)] ~ [(1) (2)~P (l):x(2)], = 2s(I)2s(2) .1 [(I)(2) - (I)(2)].
146
147
 s-, Bce~ Ji
paBe~
. , 's, ) 82 ,8z (S = 3/2, Ms = 1/2).
1s2, Is'2s', 2 s 2 : ,
,
,

', = 'I"('S, 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) - (1)(2)],
, , .:', .fi 1 2 .
(12.4)- , :
'I' = 'I"('S, 2s
2
) = 2S(I)2S(2)~ [(1)J3(2) - J3(1)(2)]. ~ '
( , ,
,
" ~., ).
IS ~ 1 2 (12.4) .
'1, '2, 'I': "

(l,Q
'I'('S) = 1 ', + 2 ' 2 + 'I' 3. , J;I
;, , '(1, 2,
Ai -J 3). . () , ;
. 1 l>IX
. OCHOB-i f .
- 1s22s ~u;'
1
,
, (. .
: .,
11). ,

ls(l)a(l) , .
Is(I)J3(I) 2s(l)a(1)
1 .
' (1,2, 3) == / Is(2)a(2) Is(2)J3(2) 2s(2)a(2) .
(KBapTeTHor.o) :
",6 ls(3)a(3) Is(3)J3(3) 2s(3)a(3)
'I'N(1, 2, ... , 7) = detj1sa IsJ3 2sa 2sJ3 2_l 2 2p+lal.
; f ;
:
..
.'
, 12.2.

. 1 { 1. . ,
'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)] ~ [a(1)J3(2)a(3)-J3(l)(2)(3)]-
",2 ' .
,
( ), . .
1 ..- .
- .fi [ls(I)2s(2)1s(3) - 2s(1)ls(2)ls(3)]x .

~ [2(l)(2)J(3) "'-(1)J3(2)(3)-l)(2)(3) ]}. (12.4)

:

!
H'I' = E'I'.
148
14Q
 KOM~
, ,
, '1
, j
S ::,,'(RS) = (!). . ' ; ' ,

, R' ~
::. cm

': j)j

R' = 1 '. 'j

. , ' OHO~
::: '. ,! R Qh' : ,~-
/- R' ; <; ' ...1
; ' 1 , ";
/
() ' , . . ::;
'1, \1/2> "', '/ rr j-Mepl R<J'j = \jIJ.L = I,r/1i(R)<pj, \,
;=\
tl: r :!
d 1 2 t ., :
Gc {<l, <2> , <} {\jIl' \jI2, .. , \jIn}.
n <J'j\jli {<p\\jI!, <P2\j12' ... , <J'm\jln}.
, , ':" R = IR~I ~, ." R~fl =trl/(Ilitr'J(R),.:! r,,,(R)I~I~J ... iJ!",1,
, " , ' .
. g ''::: de,t!<J';<J'j.:.<J';"I'He
, i :'' , . . >
G . .-
(11.6). , <pj. .
Xr(RJ : , ',.
1) 1 2 - I , I TO~KO , -

: Q: . ,.
Xr(R;) == , (Rj )Xrz (R;);
2) 1 2 - ,
: :
. 1 '
R =IR<P! I
R<J'2 '" R<p/ ==
Sij = .J2 [<J'j (! )\jIj (2) + \jIj (! )<J'j (2 )], =
/ / /
I, (R) I, 2j (R) ... I, / (R)( -l)q Q \.<J'J
~
<2 '., <J'/
!=
i=J j=1 =!
1
tij = J2 [<J'j(x!)\jIj (2) - \jIj (Xl)<J'j(X2)].

: si) ti} S ,
= [t (-l)q (R)r 2j (R) ... / (R) ] !<J" <2 ... <J'/! =det!r ij (R)! =.
, Si} ,
tij - I tij' , !'
lI, ( +1 ~ -1).
:
~ -
X(S; R,.) = kx~, (Rj ) +~ , (), :. .

(; Ri ) =~~,(Ri)-~,(R?).
150
151
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i ''
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( 1s 1 2s 1 s 1 ).
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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.
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; (13.1). v

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

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

q - ; (l, 2, ... , N) -
( , ;' ,
N -). ' . .
1"~

, 4

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

= ;; f- -
1 L(-l)q *(I, 2, ... , N)F'f!(l, 2, ... , N)d't,
(l, 2, ... , N) = 'I'1(1)'I'2(2)"~,.'I'~N)~,Ct"
",N!
- '1' .~I ~,a~9P, -
.~ F , : ' ,
; ;, """"",. ; , ~
~~ . , ,"~ S(I, 2, ... , N) = (I, 2, ... , N) = A'I'I(1)'I'2(2):'.'I'N(2v).
,
, ~
, ,

I I\ftf1:J
~, N*'(l, 2, ... ; N) (I,2, .... , N) ~ .
--1 " , , ' _'~
, , ~ (~
I j

oepaT~pOM ,, . , .. , P'
cl , ).
, ~: ~It
~

. 'P*(l, 2, ... , N) (-I)q,
--1_ ,
(I, 2, ... , N) = (l, 2, ... , N). .~ ,
, JS*(l, 2, ... , N)'P(l, 2, ... , N)dt ='

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

k ~(-I)qJ -l *(I, 2, ... , N)(p-l F)p-l\f!(l, 2, ... , N)d't = =..JN!J*(l, 2, ... , N)'P(l, 2, ... , N)d't=
=.JNj:J*(l, 2, ... ")(l, 2, ... , N)dt=
=> k ~(-I)q(-I)q ~*(I, 2, ... , N)~(1, 2, ... , N)d't = ' ,: =L (-l)q J\jIi(l)\jI; (2) ... \jIN (N)Avl (1)\jI2(2) ... 0/N(N")9'tldt2,.:)t,N:/

,)\\
(fJ)
1, * \\~
= JN! ~f (1,2, ... , N)F'f!(I, 2, ... , N)d't =
- , (13.3)
, ,.'
=JNf *(l, 2, ... ,N)~(1, 2, ... , N)d't.

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

f*(I,~, ... , N)F'P(I, 2, .;., N)d't= . , -
=.JNi.f *(I; 2, .. , N)N(I, 2, ... ', N)dt; (13.2) , 1'*, 2, ... , N)'P(1, 2, ... , N) d't
.
Oll .
.

, I~I .
f hi, ,ll . -
~
: " o~epaTopa hl:

154
155
 P12
fJ*(l, 2, ... ,ij)hl~(l, 2, .... ' N)d't==
- 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 =
== 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(I)\jf2 (1)g]2\jf2 (2)\jf1 (2)di1d't2'

, ;
f \jf7(i)\jfk (i)d1: i -
' "

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

J
' \jf7 (i)\jfk (i)d't;. i<j
, , . ' == L, [J f \jf7 (1)\jf; (1)g]2 \jf} (2)\jf j (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 J'(I, 2, ... , N)='(1, 2, ... , N)=AIl(1)\jf2(2) ... w'N(N), '

. .!
(N - 1) ,
Oll . m \jf] 11,

-.
.
f'*(l, 2, ... , N)2:gijJ(1, 2, ... , N)d1: == :1 , . .
i<j i

f (J )*Jd1: =
1

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

- \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 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' " f (J'(<(II' '1'2, .... , 'I'N *J(\jfI' '1'2, ... , 'I'N)d1: ::::0.
156
157
 ~ . , ~ (N - 2) I<: ,
hl; , - 0/1, '1'2 G'I, <2'
~ :f '9'-
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 '" d'tN f ('I"(G'I, <2"", o/N *'1'(0/1,0/2':'" '1if.i)dt,= ,

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

f G't(1)h1o/\.(l)d'tlf 0/2(2)0/2 (2) d't2 '" f / (N)o/N (N)d'tN = " ,

=f < (l)h10/1 (1)d't1' f ('I"(~" ~2, ..., '" ' (~ g, )'1'("'"

N "'2, "', 'l!N.)~t:~ ...
g . ~H.~ . paBH~.:
h2, h, ... , hN. ~ =f G'i (1)'1'1 (l)gI2G'Z (2)'1'2 (2)d't1 d't2 - J G'i (1)'1'2 (1)gI2G'2 (2}'1fl(2)~,~~:.,
I \ ' ,' I , ~ ! t ."~ "
: 1" 1" ')

'!1
f ('I"(G'I, 0/2, ... , o/N * f'l'*(o/t,o/z, ... , 'l'N)X . '". .' ,

x(~k J'I'o/l' 0/2, ... , o/N)d't= , 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
N' J,'I'*('I'i, 0/2, ... , 'l'N>'I'('I'I' '1'2, ... , 'l'N )d~"'71,
= 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 ] .
J'I'*('I'i, '1'2' ... , 'l'N) ( ~k '1'(0/1' '1'2, ... , 'l'N )d't;:: ~(ilhli),
N ) N

, -1
. .
J '1'* ('1';, '1'2' ... , 'l'N (~hl )'I'('I'b' '1'2, ... , 'l'N )d't=(alhlb),
,
m n- fI*('I't, '1'2, ... , 'l'N)(Lgij]'I'('I'I, '1'2, ... , 'l'N)d't=I,([iiljj]-[ijlji]),
i<j I<}

;
'*('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].
'<) .

158
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1. aTOMH~ ~ : ) 1 ; ) 1 ..,
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:

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N
14.2. ' - Lj;'Vj(l) = .
)=1

N- i 1 , )h
-
..-,., :'('" 1 Z ,) 1 1
~ l.,.;.-; - 2: --..,' +2:,- = h ; + 2:-. 2: N
F'V;(l).,- Lji'V/1 ) =Q"
'
,[=1 2 =1' ' ;<j ' ;=1 i<j '
j=1
, ,Jfe , ~611
~ N .~-:'. F'V; (1) - :

'(1, 2, ... , N) =de,tl0/1 0/2 ... 'VNI. F'Vi(1)='hl'V;(l) +

~ t,8

+ t [f ~j
j=1 '
(2)\jI) (2) d't2\Vi (1)
'12'
~,",J o/j.(2)\~i(2) ~'t,2\iI;r(i)].
. \ ; , 'i2 1 '," ':"!
(14.1)
"

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N ' , , .lJ ~
= 2:f
;=1
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, Fk ;: '
"', . J
+L [f
' ', '"1 '"2
f
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
'"1 '"2
;<j 'i2
", ,
,,'i2 f
Fk ; = 'VU1)~I'V;(1)d't1 +
I' + t[J'Vk(1)'V;(1~:j(2)'Vj(2) d't1 d 't2 _,
'

" N N _J'Vk (l)'V /l)'Vj (2)'V; (2) d't1 d't2]' (14.2)

':; - L2: jiJ 'V7(1)'V j(l)d'tj' '12 ,
;=1 j=1

,, , Q:-, 'VI . \ ."

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

J
'= 0'Vi(1)h1'V;(1)d't1 +
+L [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 ]~* =
+L [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]'~ j 'i2 'i2 ~
j 2 .
N
'12,
=f'V7(1)h1'Vk (1)d't1 +
- L j; f o'Vi'V j(l)d'tl = . "'[f 'Vk(1)'V7 (l)o/j (2)'V j (2) d' d f'Vk(2)'Vj'(2)'V) (1)'V7 (1) d't d't ] - F
j=1 + L.J '"1 '"2 - 1 2 - ik
j '12 'i2 '
162 163
 m h.
, .ti:~
ij . (14.2) ,

7 i:
" , Tei
~ . .

[f
~ u";. {;,,~, (1) + ~ '1 (2~ (2) d"'i\I) - [~: (2~, (~) 4T'~~ (l)]}
14.3. -
( ) - L L 'ji<l'v (I)UvjUi~ == ' .'." '
v,i j

-' , ~
d
= { ;,,~. (1) + ~ [f ~: (2;,~ (2) dt,~. (1) ~J G>t (2:~ (2) ,~, (1)]} ~
. ,]
~ - Lv(I)LUoJjj;Ui~'
v' }. ,;,} :,'.' " .: ; .'
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\jf ( _,'
1 N): .
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 ' +

!L

+~ t, [f '1 (2~:. (2) dt,'i\< (1) - [~: (2~:, (2) dt,~. (l)] ,

\jfj(2)\jfj(2)dV2
2 HeKOlfopoM
N
dV2' ,
U~jUVjU!Li - L LV j=1
vj == .
ji<l'v (I)U (14.3: I dq2,1'
{< 2, r ,
"" 1, :dq2/'12'
~
"

1
LUvjUj).. == o)..v' (14.3) i
j "
f
- \jfj (2)\jf j (2)d1:2
r12

164 165
 , ~, ~:
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~ , Q' . 1 f;k,;Ii~~il;
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'i f \jIj'(2)\jIj (2)d't2 u, t 7"" 6:-t.

i 1i2

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( = 1), 2 1i2
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j(1)\jI j(l) = J\jI!~2)~; (2)d~2\j1 j(1),

, , [2

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QI

( ~ <6]

::: LKj(l).
j
J = I,fj(l)
j*; .
, (14.4)
J1 It , . . , .
, \jI;, ;
. , ,
: ' ., < .
\jIj (14.4) N, ,
(N-:l) ~. , Iil ,' N ':l, ,;.
r , ,', \j!; ,
~.,.I<: , <;\. ( j, P<l;BHOrO i.
' , ~' ,
~' , \j!;(1):
(14.4)

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

166 167
 . . .' ..;. . ... . . , . i. . . )
. , "
, 'k-7 : '1'0
, ' Q \jf ki( 1) :
,' (N - 1) , \jfaC1).
\jfi(1) (N - 1) ~; '1'k -7 ' . -
. . , II/-,
I< 'Jfi(1)He ~.
( uu), Ii.,
j ri , i, , '
.~ \jfi(l) . ' N'1'. ('k-7jilj') = hak + .2: ([ak Ijj] -[aj I jk]) =;F~k'
. .1 J",k,a .
~9' , :
~
~ iI , , , Fak .
","- 10 . . , J(i:'
~')i( , .)19 Q , , .~: l15I' ' k . ~' ,
: . . J1i~
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u. Teope~a ,
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9tlII~Q:i~: (. .. 15). '.;.' '.... , ,
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:, li =Ki, .. j= i ~ ,;I" QQ: "', ~tj:,'~Ji;:
, qj
: .:..- N h.'J!~(i=J;,~;.;.... ,.N),
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-, X~ \jfa ( = N + 1, N + 2, ... ). : \jft
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14.4.. '

! F , ~.
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. IIY~. ~.I . . 6~ (! . e~ .yMepOB. .ft. .'.
l), , (
'~ : J<.:[ \jfi:
\jfki(l ( ;' ., . .

, , '.:;), , \jfa(1): \jf;= \jfi +b\jf, .. 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.
, : ,

168 169
 Jl -
, : . {'Jfi} ::: 1, 2, .,., ,
'?:. N) - -,
(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
(' i-+a IJlI ') ::: ,
, d:il ' i .... a -
'l'a 'l'i ,
'Jfi'

. ~.;
. ., . . .. . . .'. '. (' ;.-7~ IJlI ') =
( .'
;-) .,
u
, . ,
' ~ .

14.5. -

, 'l'a - ; J
, . , - ...
, (. .
'l'i, i::: 1, 2, ... , ' - (14.4)
, F ~ '1'; ::: <Pi(X. 'l'i::: <;.
'Jfi 'Jfj :::
... , N):
1,: - r.. ~
, lI
-
~ N
<pj.
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j=l
:

d I'
-.. ~,
. -. ..... " N '" .-
F <Pi(l)::: h<pi(l) + L, (! j j )<pi(l) ::: i<Pi,
.. .~, :
-
j=l
(14.7)
P~~(1) =h<p~(1)+ f(Jj -Kj)<p~(l)::: ~<p~.
' ::: L, [' [(1, 2, ... , N)::::L, [ detl'l'll 'l'2l ' .. 'l'NlI.
[ [ ... (14;1 j=l

170 171
 () - . 14.1.
~a ~~ :
~(q), F F -
{/ - - ; -
-
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-
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-++-
-++-

" I
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N/2 N/2N/2
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.," ,(,,) i=J j=1
, .('1. "~' ." ,

, , <pr = <p~ ;
- . Jij = [ii I jjj; Kij =lji].

-
14.6. -
.
,
-

N/2 ~ ~
.
: ,
.' F<Pi(l) = h<pi(l) + L (2Jj - Kj )<pi(l) = i<Pi(I).
, ',:.;':. ~~.;p',>j'.r .:w-f:~:c ?~\ '.; /':._, ~!;\J.~?f'~i.;. ;":'" 'n;.....r',,~~-i~.f'/~, ;;: .:f'' ~
- ('1' == <Pia \jf = <Pi~)' ,
+1/2 (
-1/2. , , ,
. , ,
- (Restricted . . .
Hartree- Fock - RHF). (. . 15)
- ('f'RHF) , N/2
: i (. 14.1, ).

<] (l)(l) <! (2)(2) <] (N)a(N) 14.7. -

<] (1)~(1) <1 (2)~(2) <] (N)P(N)
(14.7):
<2 (l)a(l) <2 (2)(2) <P2(N)a(N)
1 .-. ,.-.. -~
'f'RF(I, 2, ... , N)= Jiii. <2 (l)~(I) <2 (2)~(2) <P2(N)~(N)
F <! (1) == h<pj (1) + L (Jj....... - Kj )<! (1) + Lq Jj <! (1) = j<pj,
N!
j=l j=1

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

<PN /2 (1)~(1) <PN (2)(2)
<PN /2 (N)a(N)
<PN /2 (N)~(N)
=:
p~ (P~ (1) h~~ (1) + (Jj - )<pr (1) + f J;' <p~ (1) E~<P~.
j=l j=!
=:

";i\

172
 ') , n - q =
-, .
/3 - N =
+ q =
2q + n. , q
, ,
(F;j) = (Fo;JJ. o~ ]. /3.
L[ , F
-
~a

~~
F . , -
. :
ipI <7 <Pr. , ,
.
.

<7 <9. , ,
( - , .
). - Is 22s l ,
, u
- (Unrestricted Hartree-Fock - UHF).
- ('PUHF) 'I' ROHF (1, 2, 3) = det \<plsa <Pls/3 <P2s a \.
( > q):

'P uHF (I, 2, ... , N) =

= 2(IS\h\IS)+(2S\h\2S)+2[IS Islls Is]+2[ls Is12s 2s]-[ls 2s12s Is].
i

= [(<) (l)(l) ... <p~(p)a(p)<p~(p + 1)/3 ( + 1) ... ~ ( + q)/3 ( + q)] =

= det '<) ... <pfa ... <p~a <p~/3 ... <P~-p/3 ... <p~/3I

:
7, q
- q
= - Als,ls <ls 11s) - A2s,2s <2s 12s) -
9 (. 14.1, ). -A1s,2s<2s 11s) -A2s,ls(ls 12s). (14.8)

<1" O<p~" <2" <;.

14.8. - , :

{ F 2s<P2s
~lS<PIS
,-

-
= tls,ls<Pls + t2s,ls<P2s
, - - + t2s,2s<P2s
= tl s,2s<P1s
~a ~~
F F -
~ Is<Pls ' <*2. (14.9)
{P
* = t1s,ls<P1s* + E2s,ls
, , ,
. UHF , "" 2s<P2s
* = t2s,ls<Pls* + t2s,2s<P2s
*
, , -
~2
S . Is 2s :
-
~ 1~
(Restricted Open-Shell Hartree- Fock - ROHF). F" = h + J 1. + J 2. - 2. 2s,
('PROHF ) . (14.10)
- + 1/2, q - ~ 1 ~
2. =-(h+2J1s -Kls).
'11/2. , 2q 2
174
 (14.8). t ,
, et .
. 'q (!)
: ij = (ij)* , j = Is, 2s) , -
. (14.91 :
- , .~
, - -
! = 2LJihii + L{aij[ii I jj] + f I ji]},
Is, 2s. Tpe~ i ij
, , ,lo
. (14.9) , . /; -
i- ; aij, -
i j.
E2s, Is = f <P~s F\S<pls dv ,
(l4.11~
Els, 2. = f <pfs F 2s<P2s dv . *.
.
:
E2s,ls = (El s, 2s)* , Ta~'
F 1s '2' - . -. ! == 2L/;hu + L {2[ I jj] - [ij I ji]}.
, (14.11): i ij

. ,


:

f <p;s(Fls - F2s)<Plsdv = . . . . . . .

! = 2 L h;i + L hmm + L {2[ I jj] - [ I ji]} +

(14.10) 'l. '2' i ij
. . . . 1 . .

+ L L {2[iilmm]-[imlmi]}+- L{[mm Inn]-[mn Inm]},

~ ~ 1 ; 2 ,n
f <]' (Fls - F2s )<P1s dv = '2 (J12s, 1, + [2s Is 11s Is] + [2s ls 12s 2s]) = .
. ., . .
(i,j) (, n) .
,
n
.

. . . .

'f'1s-;2s(1, 2, 3) = detj<plsa <P2sf3 <P2saj, ! = 2 L h;; + h",m + h nn + Lij

{2[ 1 ] - [ij 1 ji]} +
'PRoHF(l, 2, 3) . . . .

<Plsf3 <P2sf3 ( + L {2[ 1 ]- lmi]}+ L {2[ii Inn]-[in Ini]}+

, i

). , +[ 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~ Sz(I, 2, ... , N)=
. ~
(.: , 1983) . (.: , = 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
~2
14.9. - S , (I, 2, ... N) (14.14)
Sz, -
,
- !
-2 .... ~
M s =1. ( - q).
(14.13) -
S Sz. : . 2
'(I, 2, ... , N), -
(I, 2, ... N),
8z :
~2 ~ ~ ~ ~2 (N ~
S = S-S+ +Sz + Sz = .~>-i
J( LS+j
N J+ Sz
~ ~
+Sz.
2
(14.12) ,s\ '(l , 2, ... , N) =Sz(I, 2, ... , N) = 8z (I, 2, ... , N) =
1=1 1=1
. . . . 2........ ' =s(l, 2, ... , N) = s'(l, 2, ... , N) .
(14.12) , S Sz -
.
82 (I, 2, ... N) (14.14), ,

,
+1/2 q - .
-1/2 ( + q = N). (l, 2, .. , N)
-
: - LS-iS+j. , i :::; ,
, - i
-
~:
. i >

(I, 2, ... , N) = <1 (l)(I)<2(2)(2) ... < ()

()<+1 ( + 1)~(p + 1) .. . <PN (N)~(N). (14.14)

Sz. S-iS+i i > q = N - ,

Szi +1/2,
) = ( ), -1/2, ( = ~ (q ).
( ~,S-iS+j )(l, 2, ... , N) = q(I, 2, ... , N).
1
M s = -( - q).
2 179
178
 , i j
( j ::;; i > ),

S [1
~2 (1, 2, ... , N)= 2(P-q)+(N -)+l (l, 2, ... , N)+ J '
. N/2
, j = + i,
+L's-iS+j(l, 2, ... , N) =

~
_(N + M s2) (1,
-"2 ~ ~
2, ... , N) + ~>-iS+j(1, 2, ... , N) = ~2
S 'PRF(l, 2, ... , N) =
''''1
= [2+ ~ ~
N (-"2N)2] (1, 2, ... , N)+ ~S-iS+j(1, 2, ... , N). "[ ~ +( - ~ 'I'RF(I, 2, ... , N) - ~ 'I'RHF(I, 2, ... , N)"
= 'PRF(l, 2, ... , N).
, ,
(1, 2, ... N), ~ , ,
-
~2
S , S= , . . -
, [~; -i S+ j J. - .
''''1
. .

- -
. RF(l, 2, ... , N) ( = q = . 'P ROHF (1, 2, ... , N) > q, 2q
= N/2, M s = ): , n = (N - 2q)
, Ms = n/2
RF(l, 2, ... , N)=<P!(l)a(l)<p2(2)a(2) ... <pp(p)a(p)<p!(p+l)~(P+l) ...
'" (j)i(P + i)~ ( + i) ... (j)N /2 (N)~ (N). '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) ...
!l ' RHF (1, 2, ... , N) =
= RF(l, 2, ... , N) : .(j)2q(2q)~(2q)<P2q+l (2q + l)a(2q + 1)"'<P2q+n (N)~(N)].

i, j ::;; 2q S-iS+) ,
S_;S+} RF (I, 2, ... , N) =
'P RHF .
=As-is+j<p! )(1)<2 (2)(2) .. '< ( ) ()<l ( + 1)~ ( + 1) ... q, 'P ROHF (1, 2, ... , N)
-q. j >
<Pi(P + O~(p + i)<PN /2(N)~(N).
> 2q, .
j = + i ,

S_;S+(+i) RF (1, 2, ... , N) = ~2

S 'P RoHF (I, 2, ... , N) =
= A[(j)l (l)a(l) ... (j)i (i)13(i). < () ()<l ( + 1)13 ( + 1) ...
.. . <; ( + ( + i) .. <j)N /2 (N)~(N)] =
= det/<Pla ... <Pi13 '" < <P113 ... <j)ia ... <213! =
"[ ~ + (~ - q J] 'I'RoHF(I, 2, ... , N) - q'l'RoHF(I, 2, ... , N)"

= -dt!<l ... <Pia ... <ppa (j)1~ ... <Pi/3",<PN/2~! = -'P RHF (1, 2, ... , N). = Ms(Ms + 1)'P RoHF (1, 2, ... , N) = ~(~ + 1)'PRO~F(l, 2, ... , N),
180
181
.. - OTKP~~ . 'RF 'RF (14.15)
S N/2 q , , -
, 52, ( 'UF)
n,
S n/2.
ro - . 'UF'
'2n(n)
'2 + 1 ,
( 'RF)'
(1, 2, ... , N) > q, . ,
-
~2

'UF(l, 2, ... , N) = UF(1, 2, ... , N) = A[<pf(1)a(1) ... S , . . -

.
... <p~(p)a(p)<p~(p + 1)~(p + 1) ... ~(p +q)~(p +q)] = - ,
= det l<pfa ... <pja ... <p~a <p~~ ... <P~_p~ ... <p~~I
, S.
, ,
'UF S-i S+i ;l. . .
, , i:S; ,
j> : ,
. .
-
S-iS+i'UF(1, 2, ... , N) = AS-iS+i UF(1, 2, ... , N) =
~2
S ,

= A[<pf (1)(1) ... <P~ ( )( )<p~ ( + 1)~(p + 1) ... <p~ ( + q )~(p + q)] = :

= [<? (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 =
S.
= - det l<pfa ... <PJ-pa ... <p~a <p~p ... <p~p ... <p~~I

~2
- ~ S -Si(Si + 1)
. , UHF - Ps = .
~2 Si"S S(S + 1) - Si(Si + 1)
S .
,
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:-:::----:::-_ _ _ =
S(S + 1) - Sl (Sl + 1)
(<! I <p~) - =S's+ I..~i'Si
, - Si"S, Sj

182 183
 , ,
Si = SI, + - = -f-j. ,
's. , ~,
, Cs'P s. .. . ,
() - ,
:
~2

S , S
~ ). ,
s tr
~2 ,
S, n ,
. ~ .
(1933)
.
14.10. ,

. ,
-
-
-
.
.
. ,

. ,
,
, ,
- ~. ~
,


, , , t:,
. , ,

.
, .
, . .
- +. ,
(.: , 1990).
<Pi. ,
, ,

,
, <Pi,

_
. ~
.

,
,
,
0,1 1- 2 .

+ = - {! \jf7(1)[-.!. ; - L ZA ] \jf;(l)d'tl + .

~

2 '1
-14,83 ,
+ f [f \jf7 (l)\jfi (l)\jfj (2)\jf j (2) d't, d't2 _ -12,6 . , 2,23 .
,
j=1 '12
, - Fe(C sH s)2,
-f \jf7 (l)\jfji (l)\jfj (2)\jfi (2) d'tl d't 2
]} = _ F;i = _ f-j. .
!j2 6,8, 7,2, 8,8, 9,3 .
, -
184
185
 14.11

:,1
1. .

2. J .

,
3. ? ?
, 4. .

5. . +

- 6. ~ 2


,

.~
* * ~ s= 0,3.
11,1 , .
el u -11,67 -9,02 8,8
el g -11,89 -9,03 11,2 9,3
e2g -14,42 -12,23 8,30 6,8
2 -16,03 -14,11 15,50 -
al g -16,57 -14,18 10,10 7,2

* .: u ., Deuynck J., Veillard . // Theor. Chim. Acta. -

1972. - . 27. - . 2281.

- 2 E2g[aIge~g] (

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
 15 ti
'Vi.
- (. . 14).
.

,
:

15.1.

- "
. ,
- .
, ,
.
. :
-
, .
- . .
- , , 'V/2),
( , , ,
) . . 'Vj(2)\jfj(2)dV2
,
,
, ..
dq(2),
.
,
. f f
e'Vj (2)\jf j (2) d't2 = dq(2)
~2 ~2
,
, 1,
, , . (1' 1, Z1)' 2,
- ,
, - - .
( --). , ,

- .
15.2. .
: ()
- , .
, ,

- ,
, m
.
.

-:- ,
( -

188 189
 <;
t

) (~
XI!:
, ,
).

u {<()}, J <Pi (1) = L Cl!iXI! (1). (15.1)
~(I) ~
F . , I!=I
{<p(I)}. CTapQ~"
~ .
. F

{<(2)}. epa~ .
l (
),
,
1 , -
j . (15.1)
, ( + 1)- OP~
, - ~
(, Mep~ N
). , - ~ () = - L'jiS <7(1)<Pj(l)d't!,
, \
i,j
, .

(Self-Consistent Field - S<I)F)~

, ~ N
, , ; () = LLC:iCViS X~(I)hIXv(l)d'tl +
, ! i=ll!,v
. ~ +LLLC:iCViC~jCtj
;<j J.!,V (},'!

(,
; . . 19). ,
[] X~ (1) (I)X~(2)X2)d't!d't2 _ SX~ (1)x1)x~(2)xy (2)d't1d't 2]_
- ~2 ~2
hl ( uu; . N

. 14.2), ..
- L L , jiC:iCVj SX~ (I)Xv(1)d't! .
i,j=ll!,v
.

. jl, V, , 't 1 .
, , -
. (. . 13)
15.3. ,

N
. () = LL:iVV +
XI!' , i=ll!,v
:
+L L L C:iCViC~jCtj([!lV I (J't] - [jl't I crv])-
i<jl!,v 0",<

191
190
 "
. 9. , ( ) ' .

() FC = , (15.3)
--=LVi~V+
c~; v
N )
+L L L CviC~jC<j ([/lV I ] - [/l't I crv]) - L L jiVjS~v, . (15.2)
j v ,! j=1 v Il ,
(15.3), (.
, . 2) 8-1/2.
(14.2), j, ,
}, C<j, ' FA = S-I/2F8- 1/ 2

' .

. ,
,
I C~i'
. i
C~; , (/l = 1, 2,' .
... , )

~( "'" + ~?~([~V I m;J-[~",J)- :P'j'S'" ]", = .

15.4.

,
.


,!

, P~y - .
() = R(), <).

, ,
P~y = (P~)*, .. , ,
x~, . . ,
, . , ,
, . , ,
Ei' .

-

- ,
L(F~v -iS~v)vi = (/l = 1, 2, ... , ). .
=1
(STO) m 1930- .
( . , :
- ) .
2 )n+1/2
R (r) = ( <; ,.n-1 -".
FC = 8, (15.2) n ~(2n)!

192 7 193
 , Ka~

, . -:: = (a~A + )/; = (

+ )/; Zp = (aAZA + aBZB)/Y.
, ~
, Is
,
,
.
,
~
. - ;
'r ( ,
exp(-] )exp(-l) = exp(-]- aBrl) =
);, -
. =
[
-
R}B) ( -
2) .
(GTO)
1950- . . . . .;
. : , .

TepaoB' 4/8 ( -
g(l, , n, ) = N(a, 1, , n)x'y z n e-a.r 2
,
).
1 )1/4 22(/++n)+/2'++n+/2
(15.4)

N(a, 1, , n) = ( 1[3 (2/-1)!!(2m -1)!!(2n -1)!! <)
(15.4),
1, , n - , KOTOPbI}i g(l, , n, ):
. N
(21 - 1)!1 135 ... (21 - 1). XJ.l = 'LCiJ.lg(l, m, n, ai) (15.5)
i=1
, - , ,
1, , n. . 1, , n
STO , , .
, OHa~ N
, l1 1 ( )
6-7 ( ).
, ,
, (' , ZA) 11
(, , ZB), , . ,
:
.

(l + + n) (21 + 1)
,
: s-op-
, - ..
- ,

.


. -
s-, ( ) -

s- ( Is- 2S-0)
(, , Zp) = (a~ + )/; = ( + ), - ( 2-, 2- 2z-~) .. -

194 195
 - STO-3G. ~ N . N-K1G
, ~ ,
~
. ~ , - .
~ N - l1 G
. .
:: : 3-21G 6-31G.
1) 1
( )!! n
, ! ,
double-zeta (DZV) , triple-zeta (TZ'1 . ,
; j' ,
2) , . . .
, , ; ,
; -~ ,
, - d-, 1 ,
- f-; o~ ,
'!l .
;
3) , . . ~ (DZP, TZP),
<. . d-
(
, ) N-K1G (6-31G*),
, -
. , ~ (6-31G**).
s-. ,'! ; , 6-31G(2d, f, ) ,
l . , [631/31/1] ~ 6-31G d-,
, s-, ", (- -
, BTO~ .
- , - m ,
. - : - ",
, - . , (corre1ation consistent - ), -
d-. cc-vDZ, cc-vZ, cc-vQZ. ,
, cc-vDZ [881/31/1], cc-vZ -
: 1+ 1+ 1+ 1.3 + 18811/311/11/1] .. ,
+ 13 + 15 = 14. lI
() ,. . aug--vDZ
.:. cc-vDZ
, m . ,
.
, - ( .
DZV VDZ), (TZV) .,. , ,
. ~ Jl . , 6-31G*
. .,.; ,
N-K1G N-K11G. 1 - ,
, :1 .,

196 197
 i ; ; . ), STO-3G 6-31G:
1s- " 6-31G(1) 6-31G(2). STO-3G
1 3,425251 0,154329
. ) , -0,466582 . . ( 6,6 %,
2 0,623914 0,535328 STO-3G lI -0,5 ..). 6-31G (
3 0,168855 0,444635 : -0,498233 .., 0,35 %) 6-31G(1)
6-31G(2) 0,427431 0,665449 .
'leTe
( (. . 15.1). STO-3G
1s ,
x(r) 6-31G
(. 15.2).
x(r) = , 276934 -3,425251 + , 267839 -,623914 + , 083474 ~,168855\,
2 2
0,4
.., .

. ! , lS-0
6-31G (i ,
- 6-31G(1) 6-31G(2): 6-31G 5,5 , STO-3G.
, ls-
i ; ; i
I I ; ; !

6-310(1) 6-310(2) r = . 1s-
r:
J 0,161278 I

1 18,731137 0,033495 1 1,000000,;
2 2,825394 0,234727
d<p(r)
3 0,640122 0,813757 ~ 1""0= -2Z<p(0). (15.6) ,

. 15.1
ls- ( 1s
:1' r =
. ,
q (15.6),
, lS-0,
.

0,6
0,6
0,5
0,4
0,4
0,27 _ _~
0,3

,'
2 3 4 , ..

. 15.1. :
1 - 1s- ; 2 - STO-3
. 15.2. 1s (1) ,

1
, 4 - -31G: 6-31(1) -31G(2) ('.
1s STO-3G )' 6-310 (2)

198 199
 , 6-IG (! , .
lS-0) ,
r < 0,005 . .: I ( ), .
.~
, .
i ; ; i ; ;
u ,
1 5484,671660 0,001831 4 52,964500 0,232714~ , . . .

2 825,234946 0,013950 5 16,897570 0,470193 ~
. ~ .
3 188,046958 0,068445 6 5,799635 0,358521 ~ ,
,
, ~ .
, , ~ u ,
,
-, . .
, ~; ,
, .
: STO jJ. ~ = 1,~ ,
GTO: ( - )
.
N
~(l, r) = I. CjJ.kg(PkjJ.r), .
k=!
(..
STO jJ. ~ ~ ):

N L-! /
~(~, r) = I.CjJ.kg(<XkjJ.r),
k=!
V(r) = VL(r) + I. I. 1 ml)[V,(r) - VL(r)](tm 1, (15.7)
/=0 =-/

CjJ.k ; <Xk = ~2P!k" 1- ; L -

r ~p [.
. . (15.7) Ilm><Zm I
,
Pk , ,
. J 1 . V,(r)
~
,~ 1 ,
:
15.5.

v, (r) = I. C/prnlp-2e-Z/pr2 .
,

,
, ,
. , , ,
, ~ / , nlp
. , . ~-: z,p.
,
, , . , -

200 201
 R
( , 5
)
. 4
, '.
, ' 3
.
, 2
.
.~ .


, ,

. 2 3 4 5 , ..

R
(Effective Potential - ). ' 3
,
, - .
2
,
('
) .

1) 4d- 5s- , -1
36 ( ,
2 3 4 , ..
);

2) 4s- 4-, ,
R
; (28
) ( ).; 0,4
.
. '
3-21G (a.e.~,
3 -17,87, 3d -11,65, 4s -3,47, 4 -2,23, 4d -0,58. ,
-0,4
4s- 4-, , 4d-
, :
-0,8
4d- 3d-. "
. 15.3 3d-,j
-1,2
4- 4d- , -'!
. 3d- , 4d-op-j 3 4 5 , ..

r = 0,5 . . 4 .1

0,15 0,5 .. 3d- j . 15.3. 3d (), 4 (6), 4d ()

r= 0,32 .., 4 ...... 1 ( 3-21G)
1,02 .., 4d - 1,2 a . e . J
, ( ;'"
. 15.4
~M 4d-op-
) 4s- 4- Ka~
5 . , -
( ). \'
203
202
 R v, . .
0,6 100

0,5

0,4
50 1
0,3

., 0,2

0,1

2 3 4 5 R, ..

2 3 4 5 , ..
. 15.5. HW (1) SBK (2)
d-
. 15.4. 4d- ( SBK)

, ~
. I
'
, . . . . *
.. , . , . ..**.:
HW1
SBK . HW
- , -'
SBK - .
GAUSSIAN HW Lan12, . 15.6.

- Lan12MB ( )
Lan12DZ ( ).
HW SBK d-
. 15.5. 15.1
-'
*1
, .
(. 15.6)
'
, ,
,

, .
Ti-Cl(l) 0,2218 0,2213
s- - ,
Ti-Cl(3) 0,2317 0,2318
:
s- - d- f-. Ti-C1(4) 0,2317 0,2267
, , , - 0,2162
Ti-O(I) 0,2158
C(l)-O(l) 0,1211 0,1213
* . J., Wadt W. R.// J. Chem. Phys. - 1985. - . 82. - . 270, 284, 299.
** Stevens W. J., Krauss , Bascll ., Jasien . J.// . J.Chem. - 1992. - . 70.- *1 HW; ,
.612. , - 3-21G*.

204 205
 15.2; (. 15.1-15.3). ,

*1
.
(. 15.6)
,


,: 1. 6-31G.
1(1)- Ti-Cl(2) 101,6 100,0 2.
,~ Cl(3)-i-C1(4) 161,1 6-31G 6-31G*?
159,5
3.
O(1)-Ti-0(2) 74,1 76,1 2?
4. ?
I
5. ?
*1 HW; ,;
?
, - 3-21*."

15.3'
*1 m
()6 ( = , , W), /

-
-
2'3 '
-'2 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. - . 8. - . 63.

206
 16 -
1I
. AAJI II .
, ,
110 ,
.

1- 2-
16.1.

()
)(; I Xl) = N fJ*(l', 2, ... , N)J(l, 2, ... , N)dx 2 dx '" dx N,
1950- . . - .-. y2)(xlx2I x )x2) = (16.2)
.
= N(~-1) fJ*(l', 2', 3, ... , N)J(l, 2, ... , N)dx ... dxN .

. .-. 2-
*.
:
N-
"(l, 2, ... , . -
2)()2 I X~ ; ) = 2)*(; X~ I )2)'
fP) (X{X~ ... X~ I 12 ... )
:
2) (; ; I ) 2) = -) (; ; I ) 2)'

)({2 ... ; I 12 ) =

r(Xj) = () ) ()2) = I
I
= r(XjX2 XjX2)' ,
= (~ )! * (1', 2', ... , ', ( + 1), 0'0' N)'f/(I, 2, '00' , ... , N) ,
. () )dv) ,
dv)
dxp +)dxp +2 '. dx N . (16.1)
') 0"),
:
J(l, 2, ... , N) ,
.
.
( ) .
,
2- ,

, r(X1X2)dv)dv2,
( ).
: ,
, (16.1) ,
dVl
. ( - 1)-
') 0"1, u

dV2 '2
- (. .
0"2,
):
. , -
(16.2): '

f r(xl)dx) = N, f r(X1X2)dx1X2 = N(N2 -1)

(, N(N - 1)/2 - N
* Lowdin .-. / / J. Chem. Phys. - 1955. - . 97. - 1474, 1490. ). 2-

208 209
 ! 2 (! = 2)
(16.2).
f'P* (~ I,'Qij ]'Pd't = N(N -1) 5'P*QI2'Pd't =
2! ij 2
, 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), = f[Q!2y(xi x 21 XI X2)x;=Xl,X2=X2]dx1dx 2o

jJ:
.
3, 4,
I, (il XJ) = Nf'Pf(I', 2, .. , N)' (1', 2, ... , N)dx 2 dx ... dx N , .. , N, , ,
I, ({2 I !2) =
l- 2- .
= N(~ -1) f'PHl', 2', 3, ... , N)' (1, 2, ... , N)dx ... dxN . ~
. Q

m .
Q = f'P*Q'Pd't =
= + 5Q1Y(xil xl)dx1 + fQ12y(xix21 xJ x 2)dx1dx2 +
~~ ~ 1 ~ 1 ~
Q = Qo + I,Q; +, I,'Qij +, I,'Qijk + 0.0, (16.3) + f Q123(i' I I2 )dx1 dx2dx + .. 0 (16.4)
I 2. ij 3. ijk
-, - ,

, , ..
Q _ , .
l-
( , )
2- ,
.
Q
, ,
paBH~ . .
Q -
Q
:

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

.
'* ' .

1 ~
,
- I,'Qij -
2! ij .
, , .-. ,
N(N -1)/2 , .
211
210

, -, '
, . Il 2- rt/.
' ' L - ., IlblX .
-
11
't'kp 11
't'k2 , , 11
't'k N \jf/p \jf/2' ... , \jfIN . (16.4).
, ki ~
. - ]
!(ki 1 Ij ). (13.2)
( = 1): = + "I hijYji + "I "I [ij I kl] rt/
i,j ij kl
-
1'' ' Ld't =1\jf~1 (1)\jf~2 (2) ... \jf~N (N) det 1 \jf /1 \jf 12 \jf IN 1 d't = .
= t (-l)q p;S(k, 1 1,)s(k2 1/2)" .s(kN IIN ) = det 1 s(k 1/) 1=D KL . (16.5) ,
.
1- , ,
, , ' = ' L, .
, , . .-.
:
det 1 s(k 1/) 1 , ,
, , DL = 1. ,
' 'L ( , . . .
)
, D~L = . -

.
~ , - ( -
{\jf,\jf2'" \jfM} ; . . 14) 2-
1-
(16.5)
(ll 2)\.
(2 1 2)
. 1-
, 2-
-
1- . ,
(k) (/) - , ,
(,1 Xl) = I, \jf~(Xl)\jf/(Xl)I,I,C;DL(k I/)CL!I,I 12 = .
k, I L

= I,\jf~(X,)\jf/(X,)Ylk'
k,l 16.2. ,
DL (k 1/) - , 'l' ,
k- I- ; Yik - ;
1- -. ().
v Ykk - , ,
, -
, () .
,
I,Ykk = N. . ,
k
213
212
 , C:iCfLi + L C:iCviSfLV'
V"'fL
: 1) Qj
; 2) . ~ (
, ':' ), XfL:
,
. -.:
2 f.."

. .. qfL :: (C:iCfLi + L C:;CV;SfLV ):: PfLfL + L PfLVSfLV'
. i WfL WfL
-
.
,
:
:
()
(Q) Z -
fI<; ,2 dv = L L C:iCVi f X~Xvdv = L L C:iCViSfLV = 1. . -
fL V fL V (), , .
(16.6), 1

. !,
:

e :
LLC:iCViSfLV = LC:iCfLi + LL C:iCviSfLV :: LC:iCfLi + 2L C:iCviSfLv' 1 ~ 2 , 2 , 2 - , 3 -
. , , (
fL V fL fL V"'fL fL fL<V

) :

, ~

. -
, XfL
- . 1968 .
(, '
- ). :
.
(16.7)
n.
,
. ,

. , ~ ~,
1955 . . :
* . ( ) -
,
.
,
. ,
, , . (V) ~~ ,
CYM~e KpaTHOCTe~ (W),
, (. . . . , . .
.
. . **):
,
, <Pi, * .., .. // . . -. - 1973. - Ng 16.-
XfL . 119; 1976. - NQ 16. - . 98.
** Arstrong D. R., Perkins . G., Stewart J.J. . / / J. Chem. Soc. Da1ton Trans. -
* k R.S. // J. Chem. Phys. 1955. - V. 29. - . 1833, 1841,2338,2343. 1973. - . 838.
215
214
 VA =L W . ,
;< .


,
, ..,
. . ,

. ,

, .
CTBO~ . : ,
-
. NAO ,
= L L (PS)/lv(PS)V/I'
/leAveB
, -
( (16.7.
~ ,
: ,
(Natural Bond Orbitals - NBO).
; , NAO,
, , NAO
~ ' , 1,8. NAO
, ~ .
~ ,
. ,
, . .
xoo~ ~ (Natral NAO,
Atomlc OrbItals - NAO)*. .
. 16.1,
, . .
, ,
.
,
(. . ) . cr = + ,
:
. l + C~ = 1; , - ,
; .
. cr

(cr, , 8),
;
.
~. .
, .
.
~ , ( ) :
, ,
.
, ? - cr~B = - '

, (
* Reed .., Weinstock R.B., Weinholder F. // J. rn. Phys. - 1985. _ . 83. _ . 735.
), .
216
217
 16.1
NBO ...:
- . NBO () ,
.

()
:

LDA 86 3L L 3L
(cc-vDZ) (cc-vDZ) (cc-vDZ) (tzvp) (cc-vDZ)

(cr * jFjcr)2 2 1,00 1,00 1,00 1,00 1,00

* = -2 -'---*---'--
-
2,66 2,64 2,62 2,38 2,52
*, - 2 2,27 2,25 2,25 2,09 2,25
.
N2 N N 2,87 2,84 2,87 2,89 2,93
6 : N 10 N-N 2,31 2,27 2,32 2,34 2,38
N 1,75 1,71 1,70 1,63 1,83
F2 F F 0,99 0,99 0,98 0,94 0,97

HF F 1,05 1,06 1,05 0,91 1,04

- . 2 1,03 1,04 1,03 0,93 1,04
,
99 %. HCN - 0,97 0,97 0,98 0,93 0,92
* N 3,15 3,11 3,12 3,06 3,12
(. 16.1, 16.2).
16.2
(. () ,
. 18). (
) ,
. ()

_ LDA 86 L L 3L
. (cc-vDZ) (cc-vDZ) (cc-vDZ) (tzvp) (cc-vZ)

. . 4 0,99 1,00 1,00 0,97 0,97

.
CF4 F 1,27 1,24 1,22 1,17 1,23

3, (. 1 4 l 1,06 1,04 1,04 1,09 1,06
.19).
CzH2 - 1,04 1,05 1,05 0,97 0,93
lt- 2-,
2,71 2,68 2,70 2,85 2,82
1/.J2,
- 0,91 0,91 0,92 0,90 0,97
. cr-
. cr(2s) cr*(2s) 2- 2,23 2,21 2,20 2,09 2,12
, cr(2p) 2s-, - CzH6 - 0,97 0,97 0,98 0,97 0,97
1,12 1,11 1,10 0,97 0,95
* 6 6 - 0,93 0,94 0,95 0,98 0,97
.: Bridgean A.J., Cavigliasse G., Jreland L. R., Rothory J.// J. Chem. Soc.
Dlt s. - 2001. - . 2095. 1,46 1,45 1,45 1,39 1,38
218
219
 16.3
162

()
CF4
LDA 86 L L L

(cc-vDZ) (cc-vDZ) (cc-vDZ) (tzvp) (cc-vZ)
*1 3-2 6-31G* aug--vDZ
- 0,97 0,97 0,97 0,96 0,95 STO-3G

- 1,11 1,09 1,07 0,96 1,01
2,00000 1,99998 1,99997 1,99987
- 1,00 1,01 1,01 0,92 1,02 Cor(1s)
.~

1,04095 0,79063 0,73070 0,71237

N - 0,94 0,94 0,95 0,95 0,95 Val(2s)
0,00469 0,00460
- 1,05 1,08 1,07 0,97 0,98
Ryd(4s) - -

- 0,00527 0,00000 0,00000

Ryd(3s)
C-N 3,24 3,18 3,20 3,05 3,26 0,59575
Val(2p) 0,79968 - 0,59583
2 6 -, 0,97 0,97 0,98 0,99 0,98 0,01270
Ryd(3p) - 0,64636 0,01908
- 0,46 0,47 0,47 0,47 0,48
Ryd(4p) - 0,02665 - 0,00006
- 0,75 0,70 0,67 0,60 0,54
N - 0,98 0,98 0,98 0,99 0,98 1,99983 1,99993 1,99992
Cor(ls) 2,00000
B-N 0,80 0,77 0,75 0,57 0,62 1,91622 1,85803 1,85778 1,86088
Val(2s)
N-H 0,97 0,98 0,98 0,90 0,97 - 0,00037 0,00064 0,00016
Ryd(3s)
- 0,83 0,83 0,83 0,85 0,87 - - 0,00030 0,00004
Ryd(4s)
"uu. , - () ; - 1,74126 1,81233 1,82777 1,82744
Val(2p)
.
- 0,00034 0,00019 0,00065
Ryd(3p)
1/, Ryd(4p) - - - 0,00004
+1
--1. do- '1 : Cor - ; Val - ; Ryd -
~ . 2s- 2- .

,
, ,
, 1/,
.
2,863.
6-31G*
,
aug--vDZ ,

.
.


.
4 (. 16.3, 16.4).
0,3 %.
,

0,135 .
,
. 16.3 16.4,
(
OCTO~HX NAO 1s .
):
,
2-,
. ~
- 2s 2p2,5.
1
, -
221
220
 16.4
CF 110

NAO*


C-F NAO

Val(2s, 2) Ryd(s, ) Val(2s) Ryd(s)

STO-3G 0,9695 3,44 - 7,14 - +0,56 -0,14 +0,41 -0,10 SI,04p 2,40 Sl,92p 5,22

.~ 3-21G 0,9373 2,730 0,085 7,295 0,014 +1,18 -0,30 +1,08 -0,27 sD,79i , 94 3sD,01 Sl,86p 5,44

6-31G* 0,8989 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

aug-cc-pvdz 0,8830 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 (
................................... 41,40010 (98,5717 %)
................ 0,50637 (1,2056 %)
= , 5182 + , 8553XF, ......... 0,09352 (0,2227 %)
XF : ................................................................................ 42

= , 5000(2s) + , 0025(3s) + , 4980(2 + 2 + 2pz) + ,

+0,0302(3 +3 +3Pz)+0,0330(dxy +dxz +dyz ), , s3_

. ,
XF = , 5106(2s) + 0,0178(3s) -- , 4957(2 + 2 + 2pz) + -
-- , 0008(3 + 3 + 3pz) + , 0243(dxy + dxz + dyz ). .

, [Fe(CN)6]4-.
(!PF), B3LYP Lan12DZ,
1,98736 3s 3.
. 16.5.
( )
!PF = , 8597(2s) -- , 0097(3s) + , 2948(2 + 2 + 2pz) +
.
+0, 00 17(3 +3 +3Pz)--0,0064(dxy +dxz +dyz ), -

1,93510 4s, 4 3dx2 _ y2 F()

- F. , d .
t2g
*- - ( -
0,12659) 3-15,5 /

222 223
 . , 1 (. 16.6). C-N
n- 3d(Fe) 1 )
"--7n*(N-). . 16.5 n*- CN-. . 16.6 ,
. , 3d,,- 1 NAO ,
NAO 4s. I (
- Fe(II)-(N-) xo~ ).
~

16.5
1.

: 11S, 21S, 2 S,
3
[Fe(CN)6]4-
1; Is2s.
NAO N* NAO N* 2.
- .
s Cor(3s) 1,98681 Pz Ryd(5p) 0,00335 3. 0,96[ <l <Pl~[- 0,28[<2 <P2~[
s Val(4s) 0,44483 dxy Val(3d) 1,90860 (1[I).
4. 3, -
s Ryd(5s) 0,03222 dxy Ryd(4d) 0,00253 ,
<l <2
(3) 1,99787 dxz Val(3d) 1,90860 5. NBO 0,7071 +
+ 0,7071piC2). NBO?
Ryd(4p) 0,02653 dxz Ryd(4d) 0,00253 6. NBO -
Ryd(5p) 0,00335 dyz Val(3d) 1,90860 - 2,22 ..;
0,146 ..
(3) 1,99787 dyz Ryd(4d) 0,00253 (/) .
Ryd(4p) 0,02653 dX2 _ y2 Val(3d) 0,95426
dx2 _
Ryd(5p) 0,00335 r Ryd (4 d) 0,01242
Pz (3) 1,99787 dZ2 Val(3d) 0,95426
pz Ryd(4p) 0,02653 dZ2 Ryd(4d) 0,01242

* . 16.3.

16.6
q ( )
(W) [Fe(CN)6]4-
NBA

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.
CN-.

224 8 I\
 17

, () = V'(r) - V(r)

II
, .
. 17.1,
,
17.1. .
F(r) ,
. 2 , ~ -
, . ~ ,
~
.
)

- , TOMY;j
, Bpe'~
. BpeW! .
"
. , (-
, J )
. - ( .
) .
. , 2
(. . 16):.: ,
155 /, . . -
.
= IhijYij + II[ii I kIJr~/.
i,j i,j k,1 (. 17.2) , 2
(-198,668764 ..) 160 / ,
(-198,729914 ..). ,

, - v, F,
, . . 300
.

, 1
(), 2
,
200
. , V(r) ,
ls- ,
r , 100

J
V(r) = (1s(r'2dv' /Ir' - rl

' , ls-
, 0,2 . -0,15 -0,10 -0,05 0,05 0,10 0,15 ,

Z. ,
z r , J
. 17.1. V () = (ls(r'2 dv'/Ir' - rl (1)
F(r) == 1/1 - ' 1(2)
V'(r) =1/Ir - r'l.

226 227
 , ..

-198,4
__-----1
17.1

-198,6 -54,6122
, . .

-198,8 Do, 9,760

1
(" - 2358,07
-199,0 , -109,5884
\
=
E(N 2) 2E(N) + Do + (0./2, . .
1,0 1,5 2,0 2,5 3,0 3,5 4,0 4,5
R(F-F), EN/, . . -0,02732
-0,05464
. 17.2. , ,
(2E N), . .
- (1), (2)
(3) -109,5338
Ellonr./(N2) = E(N 2) - 2EN', . .
. 17.2 , :r(
- F (N 2 ) -108,9956
: -) = 4,7 .
, . .
-198,326917 .. - , ,
. -0,5382*
, , Ecorr(N2) = Enonre/(N2) - EHF (N 2), ..
2 : -:: -0,1660 .. =
N-N - -4,517
, .

* :
, -0,3722 ..

.
(
,
,

).
, 98 % .
,
130 / ( . 17.1*.
) 154 / (
.-.:
);
,
. . 17.2 ,
,


, (0,145 ).
-
,
.

,
.

(Eeor)
.. -
, -,
:
* .: . - '
Eeor = - 1987. - . 59. . .. ,

228 229
 - , -'
.
, , ,
, -
,
*:
, . 14.2. ~
. ..; R ....................................... Re 1,5Re 2Re
-; " . ...................... -0'148028 -0,210992 -0,310067
(. . 16) ..: .
r , ..
J' . , ..., , ,
, -;:
,
. , I .
, 1j
,
. ~: 2 . 20.
~.i
- . - -{ ,
. .
":
,

,
(. ). ~ :
. l ,
<4
- , , KO-i - +.
. : -
- . CKa~
,
-;
.
: - , -. .
(,


.
).

,
- ( ,
(
) :
).
. ,
(
.
) . -
, , - (
. -) -
,
. ,
. , - .

. - 17.2.
, -,75 . .
: -1 . .
,
,
- {'I'i}' N-
7 - , ,

. ,
* Ha"ison R.J., Handy N.G. // Chem. Phys. Lett. - 1983. - . 95. - . 386.
230
 'i
1
;;-; 1'1'1'1'2 ... 'l'NI
= ~N!
'.
{'I'J
l Q (I, 2, ... , N) = I,Q(l, 2, ... , N), (17.1) -. ,

, i,j, ... (i,j= 1, 2, ... , N),

() - , , ... (, = N + 1, ... , 2,
(17.2~ - ).
,
- ~. ,
- - {'I'iH - 'l'i, 'l'j, ...
, - - 'l'a, 'l'b, ...
(1,2, ... , N). ~ 'l'i, 'l'j, ...
, 'l'a, 'l'b, ... ,
~ - . -
( ). (1, 2, ... , N) ':
7, - f/, -
u . (17.1) ,
- ( -
ijk ..
),
, ": .
, . - S, -, -
(17.1) - D, , Q ..
CKQ , , :
-, ;
:..:
. , ~ (OIHIO) (OIHIS) (OIHID) (OIHIT) (OIHIQ)
, (SIHIO) (SIHIS) (SIHID) (SIHIT) (SIHIQ)
- .
, ( - (DIHIO) (DIHIS) (DIHID) (DIHIT) (DIHIQ) (17.3)
) -. (TIHIO) (TIHIS) (TIHID) (TIHIT) (TIHIQ)
. (17.1)
,
{'I'i}:
, -
. ,
:
()
,
, .
(
, -
),
. (17.3)
(). ,
,
u (Configuration Interaction - CI). (OIHIO)
(OIHID)
I
(SIHIS) (SIHID) (SIHIT)
.
. (D/HIO) (DIHIS) (DIHID) (DIHIT) (DIHIQ)
,
(TIHIS) (TIHID) (TIHIT) (TIHIQ)
(reference). m
-

232 233
 , , -'
.
, '
, ,
.
N 2 -.

!
( CIS),
,
.,
.


.
(0IH10) ]
. !
( (SIHIS) . -

,

, , .
= 1 - F
, CIS ! (17.1)
. ~

.,
. (2)!
(SIHIS) N!(2M -N)!'
. ,
, -
. . .

,
CIS. . ( ) -
(,
CI, ,
, .
(CISD) (CISDTQ.


, CID (Configuration Interaction, Doubles); . 17.2.
, - , CISD 95 %
.
CISD (Configuration Interaction, Singles and Doubles);
-
CISDTQ ,
. , CISD

17.2

NM NNMM m * , CI
' CISD = + I, I, i7 + I, I, I, L ij 7/ . , %
i i <j <
CISD CISDT CISDTQ
f! - ; - 94,91 - 99,97
.
2 94,70 95,47 99,82

N 94,44 95,43 99,84
I!.
Ij

(S IHI ) . HF 95,41 96,49 99,86

* 100 % , FCI.
( Configuration Interaction -- FCI),
: Harrison R.J., Handy N. . // Chem. Phys. Lett. - 1983. - . 95. - . 386.
234 235
 17;~ , ,

CI ",1 , . 12,

~
CISD CISDT CISDTQ FCI " _ 1<P19 a <P22~ 1-1 <P19~ <22 I
568 - 28698 132686 sim - Ji
'

2 361 3203 17698 256413 ,

--1
N 461 4029 19925 137321 , ,
: l 2
HF 552 6712 48963 944348 , 2
, ( )
* .: Harrisan R.J., Handy N. .;; Chem. Phys. Lett. - 1983. - . 95. - .: - 12
386.
I
(. 17.3), , -
. .
.i
. - .
. .
(
), (
). 17.3.
CI.
, ,
, -'
. ,
(MultiConfiguration Self-Consistent Field - MCSCF)
, ( ,
) - (Configu- .
ration State Function - CSF). , , ,
CI. I
( . ,
- C2v ) -246,483752 . . :
GAESS. 1) -
<P19(al)
<22(2 )' , ;
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 J . , ,
, ,
, ,

= 0,97257 (1 <P19 a <P22~ 1.121 <P19~ <22 1J= , 97257 sim' . :

, ~ -

236 237
 . (
) , <l'*' = <l'* cos 8 - <l'*; Sl
. 8.
.
,



,
MCSCF, .
.
r f (;' d't = f ( cos 8 + 7~ sin 8)( cos 8 + ;~ sin 8)d't =
CI,
, , , = cos 2 8f d't+ sin 2 8f 7~;~d't+
- .

- ,
+cos 8sin 8 i~d't + f 7~d't J.
.
,
:

<1'; = <1'; cos 8 + <l' si 8. f i;' d't = f ((; cos 8 + 7~ sin 8)( cos 8 + ;~ sin 8d't =
, 8 - . =cos 2 8f (;d't+ sin 2 8J 7~;~d't+
,
<l': +cos8sin8[J (;;~d't+ J 7~d'tJ = 1.

<I'~ = <l' cos 8 - <1'; sin 8. , i~

.

8

, , (COS8 -si8J
( <I';<I'a ) = (<I';<I'a) sin 8 cos 8
= J 'd't+ J d't =sin8[J ;~d't+ J 7~d'tJ =

= x[J i~d't + Jr~d'tJ,

<1" = <l'U,
U- . - () .
, ( , )

U+ = (COS8 Sin8).
-sin 8 cos 8 (17.4)

<l'!
(17.4). -

- , (17.4)
:
<1'; = <1'; cos 8 + <l' sin 8,
~* <I'~* - . -

238 239

.
G- ,
,
- , . MCSCF
.

~
Xpq ( ).
, MCSCF
(17.5),
. (17.4)
,
- -1
BeHc:r;Ba =X-GH .
,

.
J~i~d't, J7~d't,
, - .


.
. ,
,
, ,
.
- ,
.

, . MCSCF,
(Comp1ete Active Space
Se1f Consistent Fie1d - CASSCF).
:

1) ;
2) ( i,j);
3) ,
( , ).
, q.
:
- ,
.
= _ () / () .
2
2, -
(17.5) .
2
,
,
. . ,
, ,
(17.5) , (Comp1ete CI). ,
, .
, .
(17.5), ,
. , .
- , - () CASSCF
n ,
(n - 1).
.

240 241
 - . , -. J
, ; j
, (" ,1

>- 1 >::: (1 +1' +1-1'2 +l

+ ...) I },
) , . j\
'1'
, .,.! 1 - 2! 3!
. , .l:1
, , '1 ::: 1'1 + 1'2 + + ... ,
, , .1
~

, . , : l ::: Ltt ti ,
, B~ ,",

, . .!
I 1"; -
~ ta tab
CASSCF. : , i. i, ij , ...
. . . CI, ~
10-12 H~
, . ,
, ,

CASSCF ,: ::: 1'1 + 1'2,

, (Single) (Double) <S:CSD).
, ,
. -. aHT CCD .. ~ CI,

. ,
(. ) , -
:- (Multirefe-
. , ::: 1'1 + 1"2
rence Configuration Interaction - MRCI).

~ ~ 1 ~ T~)2 ) 1 >
17.4. l'I')=I>=(1+l+2+'2(l+ 2 + ... 0=

(Coupled Clusters - )
=[1+1'1 +1'2 +~(TITl +21'/[2 +;2)+ ...] I ) =
I ,

. I =1 > + I,tf 1f) + L L tf}b I f/> + ~ ~ "~:JiatJ 1f/> +
i,a i>j a>j l,a j,b

Ci, i - : (17.8)

(17.6)
-
m ypa ~ CCSD ~,
: -, ~
. ,
(l + 2 + .. ) ::: Ltf + L L ijf/ + ... (17.7) .
i,a i>ja>b
.
,
, .
() , -
243
 Ci t i : , = -0,016409;

2 =-0,064232; t, =-0,011603; t2 =-0,064367. ,
Ci
1 ':) = 1 > = + 1 ) 1 ) :::: 1 ) 1 ) = (i' , -2,875263 . .

=1 ':) I ':), ,
.

( ( ).
CI :
( - ) I ':) = .
~ ~ ) )
':! = (l+ +) I I , - .

.

(17.7), (17.8) ,

CI .
f ( - )':eed't ( lil - \ ': ) = .

. CISD CCSD I ':> m
,
- :

': eeSD = [1 + i\ + 7'2 + ~ (7',)2 JIcrg(X crgPl = ( lil - \': ) = ( \ -\(1+7" + 7'2 + ...) )::::
= Icrg(X crg~1 +
= ( I\ ) +( I\7" ) +( I\7'2 ) +
+t,lcrg(X ay~1 + t,lcru(X ay~' +
+( \il\7' ) + ... - ( I > - ( I 7', > - ... =
ay~1 + ~ t? '( au~' + ~ t? 'u( ay~1 =
+t2 Icru(X
=E HF + L L t{j( I 't/> - = . (17.9)
;; Icrg(X ay~1 + '( crg~1 2
i>j >

= Icrg(X crg~ I+ ",2t, .J2 + 2 + t, )lcru(X cru~l,

,
,
,
-, ;
, .


,
( m ).
,
EHF + L L t{j( 1 ,!/> = E HF + ~ L t{jb(ab I ) = = E HF + E cor
i>j > '>} >
, :::: .J2t,; 2 :::: t2 + t?,
,
+ (
STO-6G,
Ecor = LLt{jb(ab I ).
) i>j >

244
245
 N - ,
(17.9) ( 1 (f 1, (f} 1, ... , j
:
-
~ N ~

(f /- /' ) = , = l-Fi.
i

(f/ / - / ') = , 'P Q, -

'P HF ,
( :
~ )(
(t7, t'JJ, ... ) ...
' Q = EQ' Q'
. ..,
". MeTO~
CCSD, ,
(Triple) , ':
( CCSD(T. N
, , , () =l-E.i'
I
'
(, <Pi, <)
hj,
,
**. ' - :

17.5. () + E(l) =('P HF /HO\'P HF ) + ('P HF \W/'P HF ) =

-
. - ~(~HFI~Fil~HF H~HFIH -~Fil~HF) ~
(n, n - ,
). =('P HF /H/'P HF ) == E HF
,
.

,
- ('P
HF).


W F(r) (. ). \( ' HF \W\ qt Q )\2
(2) =- l- ~------:=-----'-
Q EQ - F
__ .......... N __
W=H-l-Fi, ,
i , .
, qt Q
*
: / J.,
, ,
Head- Gordon ., Raghavachai . / / J. h.
'P
HF .
Phys. - 1987. - ,
. 87. - . 5968. 2
** .: Crawford . D., Schae-
fer . F. / / Reviews in utatinl histry. V.14 / eds . . Lipkowitz, . . Boyd.- . -
N. .: Wiley and Sons, 2000. , -

247
246
 (3, 4) l r ..
!
2,
4. 1
2 02
.

CASSCF.
K~ CYMMY~H~KOTOPX , >-----0
-0,30 L--L-_ _~_ _- L - - - - ' - - - - : - : - -
,
20 60 100 140 180

~ . ,

. 17.3.
, ,
:
.
1 _ CCSD(T); 2 - 2

17.6. , ,
-

.
3. . 17.3,

(6-31G, 6-31G")
.
50 - 60 % ,
1. -0,3 .. (
.
200 j). ( cc-vZ),
~
,
. , 4-5,
.
.
4. , -
CISD, . 17.3,
, ,
,
, . 18.
.

~ ,
.
1.
CASSCFjMP2
?
2. -
. I
?
, 3.
, I ?
, 4. () -
.
?
2. 5. . 26
, ,
. CCSD (jJt9(at) (jJ22(b 2).
, CISD. , (Ms = ).

, . -

248
 18 ()
, V,
A7IA (..
) .
,

.
,
(
18.1. , ,
() L
l.JjI0-
(Density Functional Theory ~ (, )
DF) ,
-
- ";
1920- . . . . ('1' I Z 1'1') = ()].
- , ..
.

, ().
-'
,
.
-.
(() ).
,
- (1927) .
m : ,
(
"" CF J(r)5/df, , , -,
),
U =.!.JP(r)p(r') d-d-'

2 '-'I ,
().
- .
, ' - ; CF = (3j10)(31t 2 )2/ = 2,8712. . ill ,
I:, . m - *. -
,
VX<X () (
(1 J,) , ,
1/3:
,
).
- ( 3 _ )1/3 _ ( 3 1/3 ()
VXai(r) = 6 41tPi(r) ; VX~,J.(r) =6 4n P,J.(r) (18.1) - (EHF )

= + V,
2/3 1.
1964 ., EHF = + VH + Vx,
m - *.

* Hohenberg ., Kohn W. // Phys. Rev. . - 1964. - . 136. _ . 864. * Kohn w., Sha L.J. // Phys. Rev. . - 1965. - . 140. - . 1133.
250
251

VH , ~ - - l ( ) ,
~
. V(f).
Uj
-
VH ~ ~o, , : ~I
(18.2)
~o = - . 1 . ,
. ,
, ~ ~
J[ , , .:

: ,
, - - .
(18.2)
- - - ()] , -
, .
- (. . 15). -'
,
EV(f)[p(f)] = fV(f)p(f)df +
[ () 1 ,
[ () ] . - . + [p(f)] + ~ f p~~r,;) dfdf' + [()] ;: : . (18.3)
, V(f),
, (18.3),
( - ~),
[p(f)1 = IV(f){5(f)dr + 7Q[{5(r)1;::: . (18.2)
~
->
V(r)
(18.2) Vef, ,
, ', :
:

8P~) [()1 - , v;,j () = V (r-) + f ' _r 'l d-'r + (-).

-(-')
r ,
Io[P(f)]df ().
.
() - - , ~YK
: .

8F[f(x)] = F[f(x) + 8f(x)] - F[f(x)1 = f ~f(x)dx () = f fxc(p(f)dv,

8f(x) .
() - fxc(p(f) - , B~ .?
( fxc(p(r
N
; () = L 1Jj(f) 12. ).
j=l ,

N

(-~Ll+V(f)-j }j(f) =0, () = L 1 Jj(f) 12.

j=l
253
252
 - 4 18.1

LDA GGA
- - -

'l

, ~ -
LDA S

I'r (. -
, . . (18.1))
r, . .,
.~ - ' 86, Becke . // J. Chem.
(Local Density Approximation - LDA) , ( 88 Phys. - 1986. - . 84.-
, 01 .4524

. !fJ Becke / / Phys. Rev.

. . - 1988. - . 38.-
.3098
~\
(Generalized Gradient Approximation -:-j PW86, Perdew J. ., Wang . / /
G~: j - PW91 Phys. Rev. . - 1986. -
.33. - . 8800; 1992. -
1
[] = (){(), Vp(r)}dr, .46. - . 6671
-, - LDA VWN Vosko S. ., Wilk L.,
. - -- Nusair // Canad. J.
[] '" - Phys. - 1980. -
.58. - . 1200
: [] [] -:
. I:I 86 Perdew J. . / / Phys. Rev.
(. 18.1). . - 1986. - . 33. -
.8822

LYP Lee ., Yang W,
( --- " R. G. / / Phys. Rev.
) . - 1988. - . 37. - .785
.
, - .
:
-1,0269 .. -, -1,0257 ..
' -12,126 -12,148 ..
~ ,
s(r) = ';~'(~) - . ;: -0,8846 .. -11,043 .. .
, , ~
, SVWN -
/(s(1) :
- . ,
,
/(s(1) = ~(S(f)2 .
.
1 + 6~s(f) sin h-Is(r)
- L:
~ (~ = 0,0042)
- == (1
- )ELSDA + "rlI JEHF
X
+ 88
+ EcLYP + (1- )E;vm ,
{) = 0,20, = 0,72, = 0,81,
?'i4
255
 18.~ , .. .


.
,
1 , , ,
.
- , - 1 -,

., ,
MO~_'
,. -, , - - - ,
- - - , I
,
RP -76,053 0,0941 106,2 1726 4243 4142 2,196 . . .
* ,

2 -76,279 0,0960 103,4 1640 3979 3858 2,259 (),
.
SVWN -75,898 0,0971 105,1 1520 3819 3708 2,214 ,

3LYF 105,1 .
-76,422 0,0962 1610 3894 3792 2,159
,
( )
- -76,438 0,0958 104,5 1648 3943 3832 1,854 -7 .
-
, . ,

() 'Vi(r) ~:

(, N,
)
!!,.E~88 - . , (j.!-
B3LYP m ; !ly- ). ~

56 . . ,
,
- S,VWN B3LYP (. 18.2, - .
6-311++G**). :
, ,

{}] = t l d "'V7(r)[- ; : V 2 ]'Vi(r) + U[{'Vi}' {R[}, {}].

, (RHF),
, . E[{'Vi}' {R[},
,
, SVWN, , KOTOPO~
. (, ,
),
:
18.2. -
!l'Vi(r, t) = -! o'V7(r, t) + I,ik'Vk(r, [),
k
- [[ =-v R[E, (18.4)
,
, . !ly(Xv = -( / ).

, - * R., Parrinello . // Phys. Rev. Lett. - 1985. - . 55. - . 2471.

256 9 "n 257

 18.3.

( ). ,
,
,
. , DFT

, , ,
, .

,

, , *.
-
.
DF
:
. 18.1.
8( -Il()) = .
-. E[{'Vi}, {R;}] .
{R;}. , Il, -
( ), ?
- V Il

A ik - ,
.
Il = (~~) )v'
,
.

ll'Vi(r, t) = . , 8 /8\jf7 = H\jf7, -

f f
dEv = 1l8p(r )dr = Il 8p(r )dr = IldN,
(18.4) H\jfi = I.Aik\jfk' -

k

Il = ( J.
- . , N v


.
i

:
,
.
: Ili = -Gl
( ni .
(, , , n; (j",i)

).

, * : Geerling ., de Proft F.,
Langenaeker W. // Chem. Rev. - 2003. - . 103. - . 1793.
- (. 18.1).

258 259
 , !l - ,
. , , .
, 1961 ., . . .. * :
, ,
N Z: ? ,
Pa(r) ,
N-Z= n; = E(N) = n + n + n + dn.4 2
(18.5)
Q ,
,
-< - () , n = , ~ ', .
n n= \;
. , -;
; . (18.6)
. . .. DF,
;
.

. ,
=-(~~} .
, -

, , (+, Li+, Na+, Mg 2+), -

(18.5) , ,
(Cs+, u+).
: (),

(N , 2 , -) (-, R-, R 2S).
(18.6) , . . ,
, -
, dE/dN N = Z .,. .
. +1 ,

-1 (I1N = 2) I1Epabho-(I + ),

Z-N . D F
-1---.----
. . . . . *

=-

Q---t---

=-I ..

.

+1----'----

(18.6).

* Iczkovski R. ., Margrave J. L. / / J. . Chem. Soc. - 1961. - . 83. - . 3547. * Parr R.G., Pearson R.G. // J. Amer. Chem. Soc. - 1983. - . 105. - . 7512.

260 261
 19
. S
, :

S=21~=(:1'
, 19.1.

. (

,

)
.
.
, .
(,

, ).
. ,
. ,


.
. ,


(1931). 1t-
.
,
1t-,

,

1. ? 1t-.
2. ? :

. , 2,,-
? ~ , ~,
4. .
DFT? , . .
,
, . ,
, , ,

. ,

, .
,
4n + 2.

, ( 1950-1960- .) - .

.
, ,
,
.

, , , -

263
- , ~ ,
.
.

, .. .
19.2. NDO

.
- ,
-< .

.
. ( 2 r )2n+1
1-'-..:.:~'--_rn-1 -~ (19.1)
- (1952)
(2n)! .
;

MeHT~ H ii
, ..; ,
i- ,

1
. - FflV = ~v + I, PflV ([/lv I 0"1:] -"2 [/l1: I crv ]),
(. ., 1960- .) a,~

H ii

.

N
.
Pflv = 2I,C:k Cvk, (19.2)
n:- , , k
- ,
N ~ .
,
NDO ,
- - (),
( )
.
, .
, --
,
n
(Neglect of Differential Overlap - NDO), CNDO (Xi(l)Xj(1), i"/:. . , ,
.
(Complete Neglect of Differential Overlap), INDO (Intermediate
1960- . m
Neglect of Differential Overlap), MINDO (Modified Intermediate
NDO . ,
Neglect of Differential Overlap), MNDO (Modified Neglect of

Differential Overlap) .
8-1/2. ,
CNDO (. , . , . , 1965)


. Me~ ,


,
,
. ,
(
, :
,
,

. ,
). , NDO,
-
-

264 265
 , ,
. '

qB = ZB-PBB ,
19.3. CNDO CNDO/2
:
CNDO. I1
1. . Oc~
~ ,
(ZA) .
FJ.lJ.l =",,,, +( -~P","'}M + B~ ( -ZB)"{A =
2.
.

3. [11111 vv]
= UJ.lJ.l +( -~J.lJ.l } +B~ qB"{A;
, 11 v,
11:;t: v, 11 , v
:

[11111 vv] = "{ 11 , v ;

[11111 vv] = "{ 11 , v . 11:;t: v; 11 ; v

4. h 1
:
F",v = ", - "2 ", "{'
CNDO/2 ","', "{, ..
~ = UIlIl - L (jll V I JJl = U
B IlIl - L V (jl ). "{ () ,
..
..
"'{ "'{' , ,
",,,, -
, . , :
jl
. CNDO/2
VAB
"{ = ~(1 + O,06945(Y'A RA )2 '
V = ZB"{AB' 1

' ="2 ("'{ + "().
RAB .
~y = 11 :;t: v; 11 ; v ;
,

1 . l1-
~Y == PJ.lV = "2~ + P~)S",v 11 ; v .

S",v -
jl v. NDO .
,
-
.

5. , NDO, E~ =. UJ.lJ.l + N e "{ = -",.

(19.2).
v, Ne - .

266 267
 !J,E , v

IJl-A,r =-103 +1O~ =-(Ne -1)"{ + Ne"{AA ="{,

U!lJl = -~(IJl + A,r) - ( Ne - ~ )"{. 19.5. MINDO/3

~1 -
. MINDO/3 - ,
; , , . 1970-1975- .
. - ;
(19.1) -
"{ , ,
, . 1930- . .
CNDO/2
.


.
,
UJlJl , - (,
.


I', (~Jlv)
,
( ..:' ):

. CNDO/2
,
1
, "{ = -;=========:='


RJ.. + 0,25 (_1_ + _1_ J2
"{ "{
.
~JlV == SJlv(IJl + Iv) ,

19.4.

CNDO/2
INDO E'j{ = ZZ ["{ + (R~ - "( }-R J
, ,
(),
, 2s (~s)
,
2 (~p) .
. , ,
l 3.

(lNDO).
. 19.6. MNDO
INDO :
!J,E
CNDO INDO MNDO
,
FJlJl = UJlJl + I. ([!J,!J, I ] - -21 [!J, I !J,])+ L ( - ZB)"{ ; Xi(1)x/1),
= ,.
. [!J,!J,lvv]
!J, , v , !J, :j:. v ( !J, , v ) .
22 ( s-) [/lvl(J'!].
R:v = v (%[!J,v I v!J,] -~[!J,!J, I]} .

268 269
 13 s . ( = , , z)
,
+/2 -ej2 2D, (. 19.1, ).
-/2 +/2
- .

, , .
, , -

[q] [l-1a]
J[o = cos ,
V4r;
.~

YioYio = 2. cos 2 = ~ [ ~ + v'~)

S 165 (3 cos -1)] =
-/4 13 +/4 2
131
Gf) 2 Gf) 4 ,,4 ,,4
-/2

2
~ ~( +~Y,o}
Gf) Gf) , -
+/4 -/4
] - , dZ2

[Qa~] (. 19.1, ).
-
, ,
. 19.1. (-) , 2D2 , ej4.


do.~ (. 19.1, ).
[flvla'C] D, D2 :
- (. .
R, ,
: , , )
..: .
(~-

[flV I '] = :L:L:L[ MI~m' Mfz,m} 2s- 2-):

1] 12

D, = 5(4~2s~2p)5/2 ,
1
-. M1,m J3(~2s + ~2p)6
21 /2 ,
.
1

19.1. D2 ="2
3 )'/2 ~21
(
,
s-, ,

1 . i,
r:t= ,
,,4 - j,
. :

, ,

(. 19.1, ).

270 271
 Rij , N-H -
DJ , D2 fi(Rij) .
- - MNDO
: .s, U , ~" ~p, " , .
,
(19.3) , ,
.
pf
(l = , 1, 2)
MINDO/3,
. (19.3)
(Rij = )
:
= 12. '! ( )
,

1= . ,
(,
). ,
1= 1 , ,
, MNDO, -
l (Austin Model 1).
1= 2 l.
cTBo
[Qt'p, Qt'p] = [Pt'pt I Pt'ptJ == h~. ( )
IJ = 12 = .
,

[, Mt] = [q, q] = 2~+/2

2
tr f,; fi ()
2'1 2'2 J
= 2 (2& )-2 = g;,
.
--
.


13 ( ) 19 (
2

& =-- ).
2gss 3. . . (J.J. Stewart) 1989 .
p~, p~.
3 (Pararnetric Method Nurnber 3).
NDO ,
, . (
. , )
MNDO . . . .
,
:
:
, , ,
Vv~ = -Z[Il V I SBSBJ, . ,

,
~~:

,
~IlV = ~(~~ + ~~)Sllv' . 03-
~ _ (~ :f): ~~
~p, " /3, ~" ~p, , Gss - [ssjss], Gsp - [ssjpp], Gpp [ ], Gp
I
= [ j ''] , H sp = [sp sp]
EX~T = ZZ[ss I sBsB][l + exp(-R) + exp(-R )]. .

272 273
 ,
, ~ v:, v:, v: -
u ,
u -

657. . ,

", .
. ,

( ,
19.7. INDO ). :,
, ,
.~ , ,

, .
u
. ' ' , ~
[/l/ll ] u ~
[/lV IV/l] . ' , CTPYKTypa~ .

, , .
.
-
.
* 3d- 4d- 1 ~
. ~ 2s- 2- (
CINDO/S ).
2 ,
. HOCT~ N 2>
3 ( z):

19.8. ~


, . .

-1,5212 -0,7875 -0,5950 -0,5950 -0,5264

, , ' 1 Nl 2s 0,620 -0,649 0,000 0,338
2 Nl 2 0,677 -0,203
, ,
, 3 Nl 2 0,203 0,677
. 4 Nl 2pz 0,338 0,279 0,620

; , ' -- 5 N2 2s 0,620 0,649 -0,338
.
6 N2 2 0,677 -0,203
' :
7 N2 2 0,203 0,677

v;, = L (-)2; V = Lke (e- )2, 8 N2 2pz -0,338 0,279 -0,620

v;.opc = L ;[l+s(n-)]. 3 CNDO

~ ~?
4 . )

* Sizova . v., Baranovski V./.jj J. Comput. Chem. - 1995. - . 15. _ . 586.

. 2>. ) U 2 2' ?
u

274
 ~1

20 5 ,
: .
:
,
.

, ~
,
( 20.1. - rm -
. ,
. ., -; ~
1927 ., , , ?
m . ,
, .
: ~ (
,
, - ):
. , ,
,
; (
, = N[1sa(1)1s b (2) + 1sb(1)1sA2)],
) -. II = N [1sa(1)ls b(2) -lS(1)lS(2)],

, () = N[lsa(1)lsa(2) + lSb(1)1sb(2)],
. . ,v = N[lsa(l)1sa(2) -lsb(l)l sb(2)].
. IS-0
, (
): " , IV ~
, II .
R(r) = 2- " , IV ~
, , -
, : ~
. , . -
. N 1/ ~2(1 52),

. :
ls- . ,
(
,
5 = 1):
. ,
- lSa 1sb:
1
'[ = N[1sa(1)1sb(2) + 1sb(1)lsa(2)] .Ji [a(1)~(2) - ~(1)a(2)],
1 1
1sa(1) == .= R(rl a) = - l1 ,
",4n "'n '(s = +1) = N[lsa(l)1sb(2) -lsb(l)lsa(2)a(1)a(2)],
1
1sb (1) == _l_R(ljb) = _l_e-I)b. ... 'P[[(Ms = ) = N[1sa(l)lsb(2) -lsb(l)lsa(2)] .Ji [a(1)~(2) + ~(1)a(2)],
J4ic Jn
'(s = -1) = N[1sa(l)lsb(2) -lsb(l)1sa(2)~(1)~(2)],
.
277
276
 (20.1)
1
\f = N[1sa(l)1sa(2) + 1sb(1)1sb(2)] .Ji [a(1)~(2) - ~(1)a(2)],
(20.1) \fI \f
1 ( ):
\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
= 1 f[1s a (l)1sb(2) lsb (1)1sa(2)]
; , . . , Jf 2(1 S2)
, .
1 1 111111)
lSa 1sb ~
, ,
( -2~1 -2~2 - 'l - '2 - '1 - '2 + '12 + Rab
[1sa(1)1sb(2) 1sb(l)lsa (2) ]dVl dV2' (20.2)
~ = 1. ..
\f I \f (~ (20.2) ,
) ~ ,
, . . ~: , ,
(Lg D~h)' \f \fIV 1
, ..
. ,
Lu' lS lSb -
a
, : , :
.
:
, Ha(1sa(l = (-.!.~1 -l..)1S (1) = E H 1sa(l),
- .
2 'l
\fI ,
.
Hb(lsb(2 = (-.!.~2 -l-)ISb (2) = EH 1sb(2),
2 '2
\f \fIV ,
, -
- () .
ISa 1Sb ,
- (1sil)1saC2) 1sb(1)lsb(2, -
+. , 2 , :
,
\f I \f . JIsa(1)1sa(l) dV1 =JIsb(2)1sb(2) dV2'
~b ~a
\fK(\fK(1, 2) =
(1, 2)QK(1, 2), QK - !:
\f ): :

QA
= j\f}(1, 2)H\f (1, 2)dv1dV2dcr1dcr2 = I, = 2 + 2(1 S2)'
= j}(1, 2)(1, 2)dv1dv2jQ} (1, 2)QK(l, 2)dcrldcr2' :

, 1sa (1)lsa(1) d + f 1sa(1)1sa(1)1sb(2)1sb(2) dv dv + _1_

Q = - 2f V1 1 2 1) ,
, 'I '12 "
.
,
QK(1, 2) = -2S f Isa(1)lsb(1) dVl + f Isa(1)1sb(l)1sb (2)1sa (2) dV1 dV2 + S2 .
, , 'l '12 Rab

278 279
 Q . . . ~.
, , , m , ,
, ( )
Rab Q ~
: ' ,
; .
, 66 % ,
. .. ,
: :' . :r
, - . "
, 1/Rab ( s2/ Rab ) .., . ,
. ;
, .
: ,
, - ~: .
, ~ , . . -
() "
. ~ (. 20.1) , -: .
, 1,1 .., , .. ,
- . R , ,
Rab = 0,87 (
ab
. , HeKO~Opoo
- 0,74 ), .. -'
U. ( - J , 1,0 1,6875-
) 3,14 ( 4,7466 ). J .
- 1 ~ ~ -
; , j
. -,
, ! R(r) = 2~3/2e-~.
!
( ). . , .
( ) . (
20.1 ), ,
~ ~ B~e)
. Rab = 0,741 (~ - 1,1
, . . -1,139 .., 3,782
Rab Q !
(80 % ). ~
1! , ! -
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 )
2,5 -0,0127 -0,0728 -1,0706 -0,9240 ' . ,
3,0 -0,0014 -0,0363
1! (1 ) 1 (1 ):
-1,0417 -0,9626
4,0 -0,0016 -0,0102 -1,0114 -0,9812
(20.3)

281
280
 , '! ' , ~ '> ' - .
lI,g. /.. . /.. 1 00, 11 - -1
: . +1; <1' -
/.. (0,16 ( ::; <1' ::; 2n).
); !
. (
= 3,23 ) ' '. . (20.3) ' = ' + /..' (
ls- )
(R e = 0,88 ). i Z, .
)
~ ~, /.. (~
.; ~ = 1,193, = 4,02 , Re = 0,748 ). J ~ (
L z = -ih G<l'I + G<l'2 '
)
85 % .;1
. 1
, , . ,
, ';
lI,g, :::
' '
'' :: 2 ' - 1 ' -= ' - /.. ''; -=---,
G<l'I G<l'2
_1
, . I
. . '
, <1'2 - <1'1' ,
, ~ ' , : /"1, 111, /"2,
1s-bI : 1Sa Isb , 112, <1'2 - <1'1' ,
/3. , , .

, .
. , ,

(<1'2 - <1'1)'
, ,
, . , ,
_ . v
. , v
2 , /"1, 111, /"2, 112, '12,
, , ,

, . ~
. : ,
.

20.2. - e- (l+2)
. ~
- (l933) , . .
, , ,
,

. .
(5, 11 13)
, ( ~
) ,
( 0,03 ).

282
283
 20.3.
, oc~,
, . .,
. . , '
, 4,53 . R = 1,4 . . r- ( ). ; ~OT~H
( I . ., 0-
) ,
-,
~ :
-i '(l, 2) = _1 e-O,75 0"1+A2)[2, 23779 + , 80483(/-Lf + /-L~) - , 5599/-LI/-L2 - :
2 . ,
-0,60985(I + 2) + , 56906lj2 ]. .
~:
, . Ocod -
, ~ . - -
,
: KOOP~ .
I, /-Ll, 2, /-L2 (

, ) -- :

. , \:.
, - .
.!. [lsa (2) + lsb (2) ](2)
2
, ~
.!. [lsa (2) + lsb (2) ]~(2)
. '"
2
- -

: - (
~ . -
, ), -
-). , , , ..
.

1950 . . . ,
, ,
- .

.
. .
.

- , - , -
. -
,

, 3,5 4,0
0,5 1,0 1,5 2,0 2,5 3,0
,
R(H-H), ..
. -, ,
(
. 20.1. , ~eT(~)
- (1, 2)
) (1, 3) (2)
.
285
2R4
 , , ~
, (~ :
(jg). He~
lI,g. ~
, :
\f(1 1 Lg ) = .1[\f(lL g )-\f' Lg )] = ',

'P(2 1L g) = .1 ['Lg ) + " L g )] = ' '

, , .;
. ,

,
-. ,
- . ~ ~ ~
..,
. . v

,
, ,
, ':'
-,
~ 1L,g.
ISa Isb (j gJ2
= _1_ (jg ' -
1 (jgu. 1 1 (jg~ CY~ 1 lL,u. pacKp~I
, ,
(lsa + Isb)' =- 1 (ISa -lsb) \f(s = +1) \f(s = -1). \f(s = ) \f N
J2 -
( ). 1 (jgu. CY~ 1 1 (jg~ 1 -

, ..
1
1 -2 [lsa (1) -lsb(1) ]u.(l) "21 [lsa (2) - lsb (2) ](2)
1
\f'(lL ) = - 2
g J2 1 1 .
... 3
2" [lsa (1) -lsb(1) ]~(1) "2 [lsa (2) -lsb (2)]~(2) 't' 4
-0,4
lI,g
-
. , -0,8
(jg
' ,
,
, ( _ 1,2 L.J--=:~_-,-_J....---1--'---'----:..L.:::---:'-=--
0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8
). , R(-),
: \f(lL,g)
\f'(lL,g), (jg . 20.2.
, ( CI 6-3lG*):
\feL,g) \f'eL,g) , . 1 _ 11L,g; 2 - L,u; 3 - lL,u; 4 - 21I,g (
. 9. -)

286 287
 Lu. , ~ 21
COOTBeTCTB~
Me~y 1
-.
- . , F. AJlA
(
20.2). :
, ~
( ;
l 1
, i!
- . -
Lg Iu . .
.)

,
. '( Q, ) - ,
( Q). Q -
1. 'JII.
, r- . -
2. -
( Q)
1 <f>Ia <f>IJ) 1 I <2 <2!) 1:
J
E(Q) ::::: '(Q, )* '(Q, r)dv :::::
, . .
R, ..
22 H12 l
1 : : : J'(Q, )* (-L ~A;
2;
+ V(Q, )'(Q, r)dv.
i
0,5 -0,40333 3,00719 0,15968
,
1,0 -1,06600 1,15553 0,17024 '( Q, ) V( Q, )
2,0 -1,04902 -0,06602 0,20092
, ( Q)/aQk

3,0 -0,88528 -0,43170 0,23512
aE(Q) ::::: J{'(Q, )* '(Q, r)dv + '(Q, )* '(Q, ) dv +
4,0 -0,76108 -0,55903 0,26513 ~ ~ ~
10,0 -0,59597 -0,59575 0,33730

} ~ )
* aV(Q,
+ \f'(Q, )* -'(Q, r)dv ::::: J'P(Q, ) aQ 'P(Q, r)dv +
~ k
11 2,g 212,g.
3. + Jr'(Q, )* H'P(Q, r)dv + a'P(Q, ) H'P(Q, r)*dV]:::::
, ~ ?
4.
l aQk aQk
, Q, S. :::: J'(Q, )* aV(Q, ) '(Q, r)dv + E(Q, )
aQk

f['(Q, )* '(Q, r)dv + '(Q, ) '(Q, r)*dv] :::::

aQk aQk

::::: J 'P(Q, )* aV(Q, ) '(Q, r)dv + E(Q, ) aa f 'P(Q, )*'(Q, ) dv ::::

~ Qk

::::: f'(Q,)* aV(Q, ) '(Q, r)dv.

aQk

1 rl"I1i1
289
 , - ~

: 1

.
. ..
,
:

(21.1)'

F; - , i- . , , l.Jl(x) Ix=~= .
(21.1) ..,
uu. -"
, -:-i

L[-~ fl.Jl* ; dr] = _! f'* [L

2
.

; 2; ; 2 )
X) (- ~ )~l.Jldr.
J ~

L(-~ a ;)+(V -)1.Jl =0,

2

(21.2)
; 2; ; , - (
,
- , , ,
).
.

,
.
, . . l.Jl .

(21.2) Xj,
/* j: "

')+xjl.Jl*1.Jl-+
aV (V -)jl.Jl * -'} =0.
2
"{"( n
.LJ .LJ --/ * 2 (21.3)
) ; 2; ; ) ) )
;
1.Jl*:
aV(i, j) (Xi -) 2
aXi =-[(i- )2+(i-)2+(Zi- Z)2j3/2'

,
.

(V -)I.Jl* = L(~ 2~*). (21.4) 2

2; ; X;FXi + )) + YiFyi + )} + Z;Fzi + zj F7j = ~"" = V(i, ,

(21.4) (21.3)

.
-
.
, -

290 291
 , , :.

, ~ .
, ; .

. 5

= _.!.V
2
_.!.[~
2L:-JJ
J
xp.l
' E(R) = D[I- e- P(R-R,,)]2 - D.

V:!.- ; : D = 4,747 , ~ = 1,9 -l Re = 0,741 .
, . 21.1.
, .
1933 . .
( ; . .
. 22) , ,
, ,
, r
2
.=--
J aQj' ,

, , .
. , . 21.1,
0,35-0,40
. 2Re
.
1 - -1 [ LQj-
T=--V J :
2 2 j aQj .
.
V
,
.
, . -

, .
, , V,

12
2\
\
8 \
\
1 dE1 \
T=--V--R-. 4 \
2 2 dR 1 \
--- -----\;~:....~::::~.~.~.~:.::.::.::.:~=: ..::::::..:::::...
, = + V,
: -4

-8
dE
T=-E-R- -12 \
dR' '~.. _~i/
dE
V=2E+R-. 0,1 0,2 0,3 R,
dR
. 21.1. (1), (2)
V (3) (
, )

292 293
 ,

0,4 0,4

0,3
.",--
0,2
"" ''
" " ''
0,1
" "" ' ,,
.",
.", " ,, ,
-..;:
-0,10 -0,05 0,05 0,10 0,15 0,20 0,07 0,08 0,09 R,
0,05 0,06
R,

. 21.3.
. 21.2. -! , - (1)
:'
ro (2). -
1- p(R) -; 2 - CYM~
; , 4- -';
Llp(R) - CI I (. . 21.2, 4; . 21.3, 2;
1
-,!

( - ): ).
J
0,05-1 . 21.4. R ~ 0,12
0,075 , 1

, j -

( 0,025 ). I

u )

-.i
. 21.2, 21.3. -; 0,12
] 1 .... - - ...
CYM-j I \
I \
~ . -I I \
0,08 I \
]
I \
,
. 21.2, 3). - i
(CMJ
I
I
I ,\
\
, , 0,04
I \
( ) " I
( I
I
). , -! -----/.---
, '
, *.
-0,1 0,1 0,2 0,3 R,HM
!
:<
. 21.4.
* . // Chem. Educator. - 2003. - . 8. - . 1. R = 0,741 (1), 1,25 (2), 2,0 (3)

294 295
 .
III.
:
,
.
(.
. 21.1).

1. .
2.
22
?
3. (R e = 0,0741 , = 19 HM- 1)
, : )
; ) .
,
4. = Vj2 N (
?
,
):

H(r, R) = f [-~b.A J+ f[-~b.i J-

=1 2 i=1 2
MNZ2 2 ZZ2
- LL~+ L~+ L = 1' +
=! i=1 'iA i<} 'ij < RA

( ), -
.
, -

. ,
.

. ,
, .
J.l(, R) -
, EiR):

J.l(, R) = J.I(R)J.l(, R).

J.l(,
R)
-
(r)
(R). ,
J.L(, R); ,
. EiR)

297
 . ~: (, , )
5,( x/R). ,
(22.3), ,
. , , ;
'P(r, R) = L,,(R),,(r, R). .

"
:
(22.3) ,

. x/R) -~
. -,
51 . (22.1)
. , , ,
H(r, R)'P(r, R) = W'P(r, R),
vCr, R) 1 . ,

.
, ,
(r, R)

(Ev - W)Xv + L(v / /",,) = . Xy(R). xy(R):

(22.2).
,
" ,

,
,,(r, R)x/R): Ey(R) + ( (r, R) I I (r, R.
.
(. .
), -
((r, R) I I (r, R ,
- nn

(Xi)<
. a~
, (" I V'i,,> -: ,
. , " ,: .
, . 23.
,
Z.
, , ,
-
,

(22.2) 1 . (22.3) :
, '

- ( - ):

(22.3) ~ li 2 2
=---.
2 z 2

298 299
 : , ,
, ( ).
~ I oz !! ) oz ].
2

li [/
Av!! =- 2 \ v I OZ2
02
!! ) + 2 ( v . -
.
, , < ) 2 ,
. Avv -' ,
-nn ( ), , ,

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


. ,
~~~~e ~~~~:~~~~~:;~~~~~~;~~~~:~:~~~2~ ~~=~~~ ,
, .
, -
** - 2 , HD
D 2 ,
. . ,
1. - .
.
2. (22.3) (,
, ,

11Lg 2 1Lg ).
3. .
[-(1/ 2/l)Ll + U(R) + U'(R)]X(R) = EX(R), 4.

/l - , U(R)
- (.. );
:z
(I I 2) I 2
U'(R) - , Z, ,
. .

:
U(R) , U(R) + U'(R)
.
. 22.1.
22.1

112' 1ID 112' - 1
-
-


-

-

2 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. - . 41. - . 3674.

** Wolniewicz L. / / J. Chem. Phys. - 1966. - . 45. - . 515.

1()()
 23 .
: ,
.
,

, ,
(,


23.1. ). ,
.
,
, -
, , ( Q)
.
. 22,
. , , .
(, . 25.

-) ( .

). ,
,
. ,

,
.
(~~, ~~, . . , ~~_6)-


- .
, {} , (, (, (, ... , qN-6)
(, , ): , ,

. ,
() == (), 2 , R , ... , RN ). (.23.1).
,

,
(. . 22).
.
.

,

N
(J! , , F):
. :
.
,
.
.
N - 6 ( N - 5 F
) , ,
.

02
 .
.
, ~
nn 3N- 6 (
3N - 5) .

,
.
,

.


,

. , B3LYP 6-311G*
,
, (N),
,
+ DE,
'[ ( 33 ).

4
23.2.

. 23.1. : .

- ; - ; -
-

,
.
. , K~K
. 24. .
,
. ,
, (', ' 2 ), ..
,
Fd. .
.
Fd , , 2 = '2'
(

).
-
.
', ' 2 ,
F , .
d
, 2 .
,
'2, ,
, .
, -

, .
*[ Wei Z-G., Li Q.-S., ZhangS.-w. etal. // J. l. Struct.: . - 2005.-
. 722. - . 139.

304 305
 . 23.2. , OC~OBHoe,
2 I,.
-
.
80" 90"; ,
, ,
. 80" - 3cr-
R , 90" - ~ 3s .
.~ ~

, ,

. 23.2.
, nnu (avoided ssig)
.

NaCI. 2''L, ,
NaCl. ROHF, ~ Me~
NaCl
( 2 . 23.3, ).
.
N l Na-Cl , 6 . ~ ~
. , -
RHF 6-31+G* (.. .
; . 1 . 23.3, ) , (. 23.3, ).
, l''L, pac~
, 8 ,
Na+ l-. .
~ 2''L, ~
, ,
'(1'1:) = N(3pcrC1(1)3pcrC1(2 ~[a(1)p(2)-p(1)a(2)]. . ,
.
I ,

, .. , ..
-621,1 (. . 23.3).
2 -620,8 2 , 5,2 , -
-621,2 -621,0

~
q(Na)
-621,3

-621,4
-621,2
r.::::: 1,0
0,8
-621,4
0,6
2 4 6 8 10 1 2 3 4 5 6 7

8 9
R(Na-1), R(Na-1), 0,4
. 23.4.
0,2

. 23.3. NaCl, ( )
- () (6): 5,2 5,3 5,4 5,5
NaC! -
1 - 112:; 2 - 212:
R(Na-I),

306 307
 ~, - .
~ , . 23.4:
R(Na-l) = 5,24
,
q = .
.

.
(conical intersection).

.
,
, 'Pr 'Pg.

. 23.5. . 23.6.

-

~=
~ + L (]
- oXi + '" ,

i aXi
OXi - . .
(
.,.
: HNO, ).


H ik = ik + L <'? I I 'PZ)OX" , -
, ,
.
- .

:
.
(. 23.6),
, CI.

(- R ~ FC).

*, (
) - !
(transition state) TS.
R,
'.

, , ( , ! ,
: CI-R, CI-P, CI-P').
.
= + ~o [(~o? + (110)2]1/2 = [(~o)2 + (110)2]1/2.

HNO. .
=
! = ~o 2 = 110 (. 23.5). - ! 1~ . ,

308 309
 , ..
-129,5 .
,
.

-129,6
, - ,
. 17.
-129,7
,
.
-129,8 , , ,

,
.
0,5 1,0 1,5 2,0 2,5 3,0 ,

R(N-),

.
. 23.7.
(
HNO
, ).
:

(. . ), (N - 1)
C~V. . 23.7 - .
N-H (


N-O ). ( .
c
s)

' ". (. . 24). ,
'() A'(L\) ,
,
, ,
, .
.

" ( . 23.7 ).
(. . 27).

.
23.3.

-.
:

. ! = 21 hii + 1 {2! I jj] - [ij I ji]}.
ij
,

,


.
. 2
:
. ,

, ! = 21 Ghii + 1{2 o[ii I jj] _ I ji J }.
. , i ij

310 311
 hii , [ , [ij/ji] a
u
, U
ab

,
( ,
),
, , :
L

Ji = I,CJliCVi~V == I,CJliCViJ XJlhXvdv. (tj -ti)Ufj - I,I,~,kiUfl = ,ij' (23.2)

k I
Jl,V Jl,V
, L- -
h;; ;
: .
A;j,kl = 4 I k/] - [ik I j/] - [i/I jk],
ahii = ,,{aCJli .h . aCVi a~v}
L CVI"Jlv + CJl/ ~v + CJliCvi - - .
Jl,v
(23.1) L L
ij = Fija - S{jtj - IISf, (2[[/ I k/] - [ik I j/]),
(23.1) - k 1

, , L
, . Fija = hfj + I,(2[ij I kk]a -[ik I jk]a),
. k

, ,
.
:

.
C~i = CJli +oaIUficJlk +-21 oa2IUfiaCJlk + ... .
k k
(23.2)
( ) - (Coupled Perturbed Hartree- Fock
( ). () equations).

,
.
Jlk 1 2 2 Jl k
, = . +oa-
. -+- _ __ +
Jl/ Jll 2 2 ... ,
(
GAUSSIAN) .
. ,
,

.
1 ;,
, -
a CJlk _"
2
.
- f Uki CJlk' (branching space), { , 4 , ... , )
(n - 2)- .
,
, -

312 313
 1 .; . 24
:
1) 2 - [ = ,
2) _ _ _ _
- -
4 ... - - .
n
GAMESS
. ,
24.1.
, ,
,
f N , ,
, 4, ... , N ( g). ( )
(1)-(2), G = g + f.

CASSCF, =, i =1, ... , 3N. (24.1)
;
. , ,
,
.
. i :
: , , Z.
,
,
1. . :
2. ?
3.
? 1 2

4.
E(R) = + I,-dx; +- I,I,--dx;dxj + n '
; ; 2 ; j CiX;CiXj
?

5. ?
- ; R -
6.
; N -
?
, 2.
, ,
(24.1).

; , . 22 , E(R)
, .
,

, :
(,
; . . 29).

315
 ,
: .

Fij == a2V(R). ,
aXjaXj QJ.l ,
:
; V(R)
a2Q
2 ; = -J.lfJ.QfJ. == -fJ.QJ.l'
(24.2)

i; - , i; Xj, Xj -
.
,
QJ.l(t) = QS sin(jf;t) = QS sin(21tVfJ.t) = QS sin(rofJ.t).
-
; =m,V, =m j -'
at .
qj = xjJm;. (24.2) (Xj(t) = qj(t) I J)
(24.3) Lq , , ,
.
()

(10.15):
.f' _ Fij
Jij - ;;:;- - -
v;"j Vmj = f 'P~ (-)' jd'C = f 'P~i1'P ;d'C,
.

L q - , i1 - .
. qj
q Q, ij Q;
, :

3N : i1 = ilo + (~~)Oq.
qj = L (Lq)J.ljQJ.l' (24.3)
J.l=!
QJ.l . *,


, :
,

.
1 ~2 ,
2. Pk - - :
. 1) ;
2) ( )
* ., : / .., ..u, ;
..u, .. . - .: , 1972. 3) - ;

316 317
 24.2
;
4)
.
5)
3N , . .
3N . ~
- (2) (2) ZH(2)
ZO (I) 1) ZH(I)

. 3N- 0,813 -0,407 -0,305 -0,407 0,305

( 3N - 5) -
. .

~, g ;
( ) ( 0,530 -0,242 -0,265 -0,242 -0,265
Za
) . , .. ' 0,273 -0,032 -0,032
-0,407 -0,242 0,438
-: (l)

, . (l)
( 0,247 0,032 0,018
-0,305 -0,265 0,273
ZH(l)
).
0,242 -0,032 0,032 0,438 -0,273
3N - 5. (2) -0,407
- j
(2)
( , '
0,018 -0,273 0,247
, ). ' ZH(2) 0,305 -0,265 -0,032

. - ,
24.3
. -,
- 6-311 ++G** :
( ). , Lq ( )
. 24.1 .

- 0,941 , -

-- - 106,20. 1 2 3 4 5 6 7 8 9
. 24.2. 0,01 0,03 0,04 4,89 10,05 16,91 1 725,8 4141,8 4243,9
, . -
, , - 1
- 2,8 8,4 2,0 0,6 2,1
L q . 24.3. -
.
,
-
, ( :
, , , 0,047 -0,068
0,235

0,235 -0,083

0,235 -0,067 0,048

24.1 ZO

0,234 -0,384 0,411 0,571 0,541

(\)
2 ,
-0,704 0,664
(\) 0,234
Z
-0,002 0,235 -0,575 0,538 -0,387 -0,406
Z1)
0,0005503895 -0,571 0,541
2) 0,234 -0,384
(1) -0,7527656276 0,5656324605 0,704 0,664
(2) 0,234
(2) 0,7527656276 0,5656324605 0,002 0,235 0,575 0,538 -0,387 0,406
ZH(2)

318 319
 24.4
.). ,
.. Q7- Q9
( 1 725,8 CM- 1). .,j,
, , Z , , Z ,:,
Q7 Q8 Q9
Q7 (. . '
). , Q7 = 0,1 (:": , - 1
1725,8 4141,9 4243,9
, ), Z -(1) 0,035 0,719 0,732
( ) 0,0067 ( -(2) 0,035 0,719 -0,732
J ),
(1)--(2), 0,823 -0,007
Z 0,0538 ,
0,0411 ( = 0,0411),

- 0,0411 ( =-0,0411).
1 . 24.1. .
Q7 (Q7 = 0,5) 3N -6 = 3 (
. , -(l) 0-(2) H(1)-0-H(2,
-- ( ). .
Qs Q9 . 24.4
(. . 24.1). L q
-. . ,
( Q7 ,
), - .
, ( Q8 Q9 .
).
.
L q
.

. 24.5. :

(-) ,
(2,
. ). , ,
. ,
, , (

. L q , )
.
, ,

z , ( )
, .

0,9. ,
( ;
. . 24.5), 0,012. B3LYP
0,967 0,002, . . -
,
. SVWN 2
1 0,974 0,948 .


. , 111 -
. 24.1. : Q7 (1), Q8 (2), Q9 (3)

320 11 321
 24.5 . 24.2. 2,2' -
,

, - 1


-, --,
l 2 V

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
1,2
6-31++G** 0,09413 106,2 1 725,8 4141,9 4243,9
1,0
2 6-31G* 0,09690 104,0 1 735,5 3774,8 3916,2
0,8
3L 6-31G* 0,09686 103,6 1 713,1 3729,8 3851,6
0,6
3L cc-vDZ 0,09686 102,7 1658,6 3752,3 3853,8
0,4
3L cc-vZ 0,09613 104,5 1639,4 3800,9 3901,1
0,2
3L cc-vQZ 0,09605 104,8 1633,0 3808,6 3909,8
B3LYP aug--vZ 0,09618 105,2 1626,1 3796,4 3899,7 500 1000 1500 2000 , - 1
SVWN cc-vZ 0,09692 104,4 1653,3 3733,3 3841,8
. 24.3. 3L (1) 6-31G* (
0,09572 104,5 1594,8 3656,6 3755,8 0,9613) (2)

2,2' -

VZ
* . 24.3 2,2' - (
: - 0,9066, 2 - 0,9649, B3LYP - 0,9726, SVWN - B3LYPjcc-vDZ) .
0,9946. ,
.
40 - 70 CM- 1.
B3L

. , ,
.

- , 0,893**.
2,2' -. 24.6


- 2,2' - (. 24.2, . 24.6). 2,2'-,
,
(6-2G*) LVP (6-IG*) LVP (cc-vDZ)
( , -
, - , - , -
6-31G* cc-vDZ, 1,0030,009); , - 1 - 1 - 1

, 7 %.
48,0 3,8 58,4 3,3 61,2 2,7
108,2 3,5 96,8 2,6 96,6 2,6
* Ha//s , VelravskiJ., Sxh/eg/.. //Theor. Chim.Accounts. - 2001. -
. 105. - . 413.
177,3 7,6 164,9 6,4 164,9 6,0
m
** 257,2 228,3 227,8
: http://srdata.nist.gov/cccbdb/vsf.asp; http://
355,8 334,0 333,8
srdata.nist.gov/ cccbdb/vibsca1e.asp.

322 323
 . 24.6 . 24.6
(6-2G*) L (6-3IG*) L (cc-vDZ) (6-2G*) L (6-3IG*) L (cc-vDZ)

, - , - , - , - , - , -
- 1 - 1 - 1 - 1 - 1
- 1

458,9 9,9 411,6 7,6 412,0 6,9 3371,4 3 193,1 3180,2

462,9 418,7 417,7 3371 ,5 56,0 3193,2 28,6 3180,2 22,3
(476,7 447,1 447,2 0,1 3395,4 62,1 3213,8 51,7 3201,3 39,4
. 495,3 < 0,2 449,5 448,3 3395,8 3214,2 3201,6
I 622,6 572,7 575,8 3435,4 1,2 3243,3 2,9 3228,5 2,8
674,4 628,4 625,4 3435,8 3243,9 3229,2
681,8 17,2 634,8 13,3 624,1 12,4
723,1 7,1 672,2 6,4 667,5 6,3
826,0 15,9 760,1 1,8 761,3 24.2.
839,0 760,6 763,4
842,0 778,4 81,6 778,2 74,7
859,7 108,9 786,0 782,4
919,8 841,5 849,5 -
1018,5 3,3 922,5 1,7 924,2 6,0 (), (S), ( .
1028,8 931,2 933,3 :
1093,1 8,3 977,2 0,3 983,3 0,4
1097,7 982,5 990,0 S(T) = S + SBP + S + S - nR[ln(nNo)-1],
1 101,9 0,1 1 012,5 8,8 1009,5 8,0
1106,4
1 134,0

11,6
1014,4
1016,3


1010,7
1026,5

0,2 S -- n R{~ + 1n [(21CMkTJ%
2 h nRT]}
2 '
1139,9 1 016,5 0,3 1026,5
1140,2 1,3 1059,9 8,1 1056,8 8,6
1152,3
1179,2

43,0
1074,5
1096,4

6,0
1066,1
1083,4

9,8 S = nR [~ +
1 ~1C VaVbVc ] ,
2 (j
1 185,3 1121,9 16,7 1 111,0

S = n/~6[ U: exP(~o:) -1 -ln[l- (-u:)]}
1 188,6 28,8 1 126,3 1 111,5 15,9
1213,4 1 181,5 2,1 1157,9 2,3
1219,5 2,3 1181,7 1 158,4
1315,4 1293,4 1284,1 0,5 S = nNlnW,
1325,2
1413,9
11,0
1,0
1 298,6
1334,9
1,7
6,0
1287,2
1 329,4


() = + + + + RT,
1 430,1 1340,0 1 330,5 7,0 3
= R~: =:~::~I:~),
1456,3 1351,4 1 336,2
1589,7 54,2 1465,1 38,0 1442,9 39,7
1 617,6 1 491,6 1474,3
1636,0 98,9 1 506,1 76,1 1485,2 71,3 -6 hv
1672,8 1529,5 1 512,9 =N I,
:
(:)_I'
:
1 766,3 74,5 1616,7 39,6 1 608,5 39,7
1 794,9 1635,8 1627,4
1 799,9 137,4 1646,5 1639,9 91,8
1808,7 1647,9 86,7 1 641,0
3360,4 35,6 3 168,0 59,8 3149,3 52,5
3361,0 3168,3 3149,6

324 325
 25

25.1.

u hV a
= kT'

n - ; R - ~
. ,
; N o - ; - ; k -
,
; -; - ; h -

' 1 - ; () - ; -
,
~; ga - ; W - . ,
(
,
, ); - (
,
).
,
-7
, ,
( - , - )
,

1 ,
!1() = Hb(T)-() +-2 L hV a -"21 L hv~. , .
~EA
, ,
- ,
( ):
. ,
1 3N - 6
=- L
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. , -

(. . 24.4). .
4. . 24.4, . 22.
.
5. , ( ,
.

327
: -:

, , .
. ,
),
;;
(
, (
). fIa ,
, ).


, . -
.
-
( )
~ ,
70 ,
. ,
. ,

1930- ., - . ,
, , . {
. , .., . .
: -}
,: . . . (1935),
. ;

';

.
.
,

, ,
,
-'
.
. :.

, , , .
.
..
,
.
.

He

~ = - 2n~ [( I ::2 ~ ) + 2 ( I :z ~ ) :z J
. (l960-1970 .)
.,-, .., .,
.. ...
~ -
,

; 25.2.
.
( ) ,
, !l (. . 22),
, , ,
,
, ..
,

,
,

,
~ = I, (n 2
Z Z
2 2 2

ZAe
--/: ) - I,I,-+ I,-+ I, ,
. , , - i 2 i riA i<j rij < rAB
,

, -
.

328
329
 ,
~(, R)
, (

). .
.

fl(, R) = flfl(, R) ,
.
(
TQPbIX R). q
}1

' [(, R) = I.~(R)fl(, R),

fl
X~ (R) v, fl - .
, ,
. 1
,
.
ill

'(, 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 ).

1i2
=
iA
(25.1)
(, I ":: ) = ( , I ~ I , ) /(, - ,)
iA i- . ,
-,; ,
! , ..
, 1 .
. - , :
, , U(R)
. -: ,
: , . ,

. , . d = U(R),
, -'
. , ' - umuu ( d)
, -:
,
/
\ ~ I d)
; . -
. , -\
'P(r, R) -
, . -

330 331
 ,
1,6 1
U+:
~
~ 1,2
xd = 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) 1,5 2,0 2,2 2,4 q

. 25.1. (25.3) qc = 2,07:

1 - a.(q); 2 - sin[a.(q)]; 3 - cos[a.(q)]

. d _ [T~ n + v.d]
lli-Xf.1 -
d "v.d d
f.1f.1 Xf.1 + kw f.1vXv
Gt f.1;Ov
a(q) = 2:_!arctg [2(q -qc)].
4 2 W12

, q < qc,
.

(25.2) arctg [ 2(q - qc>] "" 2:, . . a(q) "" 2:. q = qc a(q)
(. . 23.3). W12 2 2
(25.2) :
1t
-, q a(q)

( ''P~ ) -(cos
1
-sin a(R)
a(R)
sin a(R)
cos a(R)
)('P
'P~'
f) (25.3)
4
(. 25.1).
. 25.1
.

(~ I :!)
25.1

( 1d I-aq
~) + Gq (R) =.
a.(q) '1 'Y d2 vd

(v2a v;a J
n/2 ' -'Y~

2
,
, ,

n/4
~ ('f + '~) _l_(_'f + '~) ~(f!Ja + V{ Via - V{ J
J2 2 f!Ja - v2a Via + Vf
') 'Y~
(v;a v{' J
qc - ; W12 - .

332 333
 ,
Vf2' ,
9
(. 25.2),
(. 25.3).

*
8
1. :
H l1 = [-0,4( + 4)],

7L-______J -_ _ _ _ ~~ _ _~_ _ _ _ 22 = 0,015{[-2(- 3)] - 2[-(- m + 0,015,

2,00 2,05 , ..

12 = 0,003[-0,5(- 6)2].
. 25.2.
: vy (1), v~ (2)
.

2.
, 1.
3. 4 . 22, -

(I I ~ 2)
. . , 1 = 6.
4. ,
. ,
(I I ~ 2) 1.

5.
( ). 1
= 6, 4.
. 25.2

. . 25.3 ,
(25.3),
( )

20

10 1
2

~
-10L-~~~__~' __~' __~'__~~
' ___
1,5 2,0 2,5 3,0 3,5 4,0 , . .

. 25.3. : v1 (1) v~ (2), -:

(25.3), ~
* Mathematica
V12 (3) ( 25) ! .

334
 26 , (26.3)
(26.1) ,
.
(26.3) -
(26.2)
. ,
:
r = .
:
, t
(26.3)
n.
. 5, ,
,
.

= hkot 1 = , ..
(26.2) Ll = .
, (26.2) -

+ Vo(x),
. ,
v = hko 1 = 1. . *,

t =

[
2
.] _2
_ __
2
1 '( t) = (1ta 2)-1/4 2 2 ip ]
__o_+---LQ.
'w(,t=)= 1/41/2exp --2+1kox, (26.1)
1t 2 , [ 2 2 4 2 4 2 2

.
-- -+ i-
1 ( Po-aJ2 -2iro( + (
- +iPoa)x
- - - -iro( -irot]
-.
[ 4 (J h h (J 2
.
,
:
ro

(26.2) '(, t)=(1t(J2)-1/4[_!(~_ cosrot_PO(Jsinrot)2 +

2 h
.
+ ix ( cos rot _ sin rot)+ ipoxo sin 2 rot +
(J h h
t

. 2

I .
+ --s2rot---s2rot--
. 2 .
l 2 .
lro t]
J
.
42 2
4 2
'(, t = ) = (a1t 1!2)-1/2 [ - ( ~a;)2 + (26.3)

= (l mro)l/2.
* . ., . ., . . . -
.: , 1981.

336 337
 I 1
iI 1 1
i
:
iI 1 1
11 1 1
11 1 1
iI 1 1
1':(, t) 12= 1 exp[-~(x - cos 0)[ - ~sin 0)[)2].
11 1 1
iI 1 1
11 1 1
(jvc (j ) 1 1 1
11 1 1
iI 1 1
iI I \
11 1 1
11 1 1
11 1 1
( 11 I \
]~ 1 1
= cos 0)[ + ~ sin 0)/, (26.4) \~ / -----------------
) I~ ;:'-~-==-=--=--=-=;;,.""=-""=-""=-~'i:."'=-'=.'=."'=-"'=-
....

.. (

) 0).
(26.4). ,

, ,
,
. :
,
.
, ,
,
.

, ,
, 0),
q
. , . 26.1.
q ()(D):
: q == q - qo. - t = ; - t = 50' 10-15 ; - t = 150' 10-15 ; - (::: 250' 10-15
,
. (.-
()(D). . m ,
. * m (500 )
()(D), HDA - 1,4--
,.--.... .
1,3- HN=CH-CH=NH ( N N): .26.1
1 '
~ ~
(dxz ~ c*(HDAB :

, ,
N N N N
- (q) -() (qco)'
q'l!q +\!-

\ \ ':(q, qco). , !l
,
q, ~e<1f~a

* Heitz . ., Guillaumont , Cote-Bruand 1., Danie! . // J. Organomet. Chem. -
2000. - . 609. - . 66. 1' ( -

339
338
 6
....................
1 "'.....
\ <.> //
/'"
'::;: 4
<.>
..... 4
6
-:' 2

..... "-1
~ 2
..........
'::;:<.> 11 /.1'. ."'. .....
//
0,2
R(Mn-),
0,3 0,4
O~~~~------~----~
0,1 0,2
R(Mn-),
0,3 0,4 ....6 4 2
4

-:' 4 2
6 "-1 3
0,2-------------,
..........
,t'!~ ""'~ ..........
~ /.1''''
~iI' III
~" 2 // 4
. 26.2. ..... /."
3
JI
6 4
,.' 0,1 -:'

..... (>(D): "-1 2

3
- (1- ' (
1

--2-._ ); 2- '; - '; 4-

""'~ ...................
,t'!~
'". _ '); - (1 - V?1 (- "'.....
'--_ _ _'-'-_ _"=-"'"::-=.="-=-=."-= ); 2 - Vg ; - V~4; '::;:<.> ~"
,t'!iI'
//
/'"
4
0,1 0,2 0,3 0,4 4 - V~2); - - ..... /.i'
2
R(Mn-), 6 i' 3
(1 - V14; 2 - V14; - V1)
-:' 4
2
..... .....
"-1
3 \
\
). ,
.

0,1 0,3 0,4 0,1 " '"
0,2 0,3 0,4
R(Mn-), R(Mn-),
,
6
.
, R(-)
- ) == . 26.3. ()
= 2 (. 26.2, ). (6) (2-4)
.
()(D) (. . 26.2):
(. 26.2, ) : 1 - t = ; - t = 3,6 10-15 ; I - t = 6,510-15 ; IV - t = 14,510-15
V12 -
cr -7 n*; V~ - dxz -7 n*; V~4 -
dyz -7n*. ( ).
. 26.2, . , ,
,
. .
dxz -7 n*, .. (. 26.3, )
Vj,
. .
,
, ,
(. 26.3, ). .

340 341
 , ..
. 26.4.
2,5 NO, .
2,0 t = (), 826 (6), 4 124 () . . , ,

(z - NO - ,
1,5
) .
1,0 :
0,5
, .
(


, ,
I
, ..
2,5

.
2,0
1,5 NO

.
1,0 ( ) 1. ,
0,5 (26.2) ,
?
NO . 2. : V(x) =

, .. -------...,
, = + 4)]. , t =
[-0,4(
= 6?
2,5
3. : V(x) =
2,0 = 0,01S{exp[-2(x - 3)] - 2[-( - 3)]}.
NO ( -
1,5 Pt-NO). , t = ) = 6; ) = 2,5?
1,0 +8q, 4. (26.2)
NO - - , = ,
0,5 = ,
8q.
1 2 3 4 5 6 7 8 - = cos(rot) + !..si(rot).
z, .. , ro

,
NO
v : ?

~ (. 26.4)*. ,
, Pt-NO,
- .
~
, -
~

.
,
-
.
,
i! ,
, -

* Saalfrank . // Chem. Phys. - 1995. - . 193. - . 119.

342
 qo.
27 E(qo). l?
E(qo) ~ ~I~
( ) ,
, .
,

.
(
,
,

() .
, , ,
, .
. , ,

.
(.27.1). . 23.
m 1931 . , ,
r. . . , , :

,
, . ,
.
. . Ta~x .~ ~
(Intnnslc ReactlOn dt - IRC).
. , -

( ) qo. qi = m}!2 Xi
,
. :

dXk / ds = gk / 1 gk 1,
.
gk - , -
5,
(. . 24).
, (. .

) .
,

s- .

,
,
. 27.1.
. . .
,
, ~
,


. -
( TS)

344 345
 1 . 27.2. ,

.
QST3 ,
.
( )
,
.
Xk Xk+l ,
'(
l ."
, -
, , ,
. . . *, ; . ,
. IRC, ,
, Xk .
2 (. 27.2). Xk
~ Xk+ 1 1. ,
Xk+ 1, &: ()
. ,
Xk+! = Xk - (5/ 2)gk / I gk I . -

xZ + 1 1. .
( -
, ,
l,4-). ,
5/2.

IXk+! - Xk+11 = s/2, ( C2v ; . 27.3).
,
. . .
,

=
( ).
.
s ( 0,4).
!l,
~,

.

,

,

, g
g
. () g g
, g g
.
IRC ,
. ,

.
~ ~ ~
1 2
QST2 ()

(). -

. 27.3. (-) 1,4-

* Gonza/vez ., Sch/ege/ ..!! J. Chem. Phys. - 1989. - . 90. - . 2154.

346 347
 ! 27.1
,::;: 0,2 ~r----------+----------~

==:
~~----------~---------. 19-24-
0..
1,4-
~~
.... ::;:

;1

0.0
-0,2

( ....
~ -0,4

19

. 27.4.
1,4-

20
. 6-31G*.
RHF QST2,
CI.
.27.4
,
: , . 27.1 -
. 21
!
, 2 -
, .

.
;
22
250 / (. 27.5).
. 27.5

,
.
He !! ! ~ ! (
<1'22 ~ <1'25), . .
.
, -
23
~
2 2
1... a?a'f.b'f.b? 1, ,
!!,
.
:
14,6 /. ,
,
, -
24

* 2
-n- 2

348 349
 -(),
/
653
1200 TS
1 R* I

.,~
550
2 460 520
.
3 ;..
-::
800 :t:
4 (!)

~ 5
r
I

400 R ()

. 27.7. (/) ,

(. . 27.6)
246 8 10

37,6 /. ,
. 27.5.
,
1,4-:
,
1 - IIA 1 ( ); 2 - IA 2; 3 - 2 I ,; 4 - IB,; 5 - '2 . ,

-.
- (. 27.6):


.

S. So
. ",
-

(SO) (S.) ....:1:... r

,/

, S,
. 27.1. ,

,
. 27.7.
(
) ,
*, TS
. 27.6. , / (. . 27.7)
. /
(2)-(4)
.. Palmer I.J., Ragozov N., Bemard F. et al.(( J. Amer. Chem. Soc. - 1993. - . 115.- (3) .
.673.

.
350 351

28
1. .
2. QST3 QST2?
3. SI
, ,
I ,
SI'
f.
14. ~
?

, .

,
.
,
, . ,
, ,
,
, -
.

,
,
.
,
,
:
- , ,

, d-d-.
:
,
, , ,
.

BpeMeHHbIe

.
- (
u ),
.

.
,

, , (. 28.1). -

12 353
 , ..

-195,9

-196,0
~_:=6_-_

~2---- ~------
-196,1 1
(
I
-196,2 '--_-"--_---J'--_---L_ _-l.-_ _~
' 0,2 0,3 0,4 0,5 0,6
So R R(Ru- ),

. 28.2. : a1A' (1), b1A' (2),

. 28.1.
1 ' (3), d 1A" (4), 1 " (5), flA' (6), glA" (7)

Ru(S )( )( 2 )(D) (
CASSCFjCASPT2); MDAB-N, N'--1,4--l,--
,

.
, .

, (. 28.2)*.
, ,
, -
. (Time Dependent
. Density Functional Theory - TDDF).
'Ia ,
. ,
.
. .
. ,
()
, : .

. , .
. .
I
. -, ,
. (
. ) .

: . ,
(multireference) (MRCI) ,
. , , . . .
m , CASSCF. - -
MRCI
, m -
* Daniel . / / Coord. Chem. Rev. - 2003. - . 238. - . 143.

354 355
 m .
28.1

. ( , )
TDDF ,
, ()
- -
, ; ,
CASSCF+ TDDF TDDF

+ 2*1 (ANO) (6-31 G*) (aug--vDZ)
ce(fb . lB2u 1[ -7 1[* 4,84 5,52 5,45
I .~8.1 4,90
lB 1u 1[ -7 1[* 6,30
TDDFT CASPT2. 6,31 6,11 6,20
I MRCI 0,5 ( ). lE1g RYd(3s) 6,38 - 6,06 6,33
*, CASPT2, lA 2u RYd(3p) 6,86 (0,07)*2 - 6,58 (0,013) 6,93
0,1 . lE1u Ryd(3p)
: -
6,99 - 6,60 -
lE2u Ryd(3p) 6,92
-
[4s3pld], [2s1p], - 6,66 6,95
lE1u 1[ -7 1[* 7,02 (0,82)
8 - 13 s- 7,38 (0,12) 7,00 (0,12) 6,94 (1,05)
6- 8 p-. ,
'Jc .
, .. Roos ~., Fu!~cher ., Ma!mquist .-. et al. Quantum Mechanica! Electron
C6H~ 1995 '2 CalculatlOns wlth Chemical Accuracy / ed . S. R. Langhoff. - D d ht . 1uwer
Structure
. . . ,
3s- 3d-
, ,
28.2
.

(m , )
6-31G* , 0,6 .

( aug--vDZ)
-
()
. - -
:
- - SVWN 3L*1 3L SCI*J SCI -
( ( (- ( (-
CASPT2*J
1) 1t- 1t*- *2) ) pvDZ) ) pvDZ) (ANO-L)
( -? 1t*-); lA 1
2) 1t -7 * 6,16 6,19 6,53 6,45 6,68 6,42 6,38
1t*- (n -? 1t*-). lA 2 n -7 * 4,29 5,07 5,06 6,79 7,34 5,17 5,43
(. 28.2) lB2 1[*
1t -7 5,35 5,47 5,73 6,10 6,38 4,86 4,99

lB l n -7 * 4,20
( 4,76 4,86 6,16 6,09 4,91 4,59

B3LYP). I 2 n -7 * 4,18 4,93 4,84 6,66 7,10 - 5,40
(SCI)
2 1t -7 * 4,52 4,47 4,69 4,63 4,90 - 4,84
. TDDF

l 1t -7 * 4,48 3,91 4,02 3,53 3,60 - 4,1
CASPT2.
l n -7 * 3,37 4,05 3,98 5,12 5,02 4,1
. 28.3 initio
r- 0,67 0,32 0,38 1,04
TDDF . 1,22 0,22 -
'
,
.
'1 ~HHe .: Bauernschmitt R . Alrichs R. // Chem. Phys. Lett. - 1996. _ V 256 _
. 454. (52111/411/22J' . Sadle'; // . Ch:
* Roos ., Fulscher ., Ma/mquist .-. et al. Quantim Mechanical Electron Structure Acta - 1991 - V 79 *3 ,.. ,. eor. 1.
Ca!cu!ations with Chemical / ed. S. R. Lal1ghoff. - Dordrecht: 1uw, 1995. . '" - . 123.
.

356
357
 28.3 29


Ru(S)z()z(D)
Ru(S( 6 s >)z()z(ID)

-
( CASSCF/CASPT2 TDDF, L ,
: ." , - 1
/(' )
, - 1 f , - 1 f
!! 21260 0,17 22020 0,063 18900 6050 [Ru(>]2+
( d~ 2,2'-
!! 24630 0,005 24680 0,006 25000 960
(). -
1 1 29220 0,13 29760 0,042 32260 38500 445
- d1t -
1 1 32940 0,003 30410 0,01 -
,
bI B 1 33930 0,018 32182 0,002 - - * - 2,2' -.
38640 18700
1
1 37330 0,005 36540 0,098
(Metal to Ligand Charge Transfer - MLCT). m ,
d 1B 1 38360 0,13 37590 0,045 - -

1 2 39640 0,003 39760 0,004 - - ,

[Ru!Il(bpY)2(bpy-)]2+.
eI B 1 - - 38630 - - - ,
uu. IPDAB - -I,4--I,-; - ,
, CM-1; - , /(' ); f - 10 CM- 1. ,
.

. ,

1. CASMP2?
2. CASSCF .
? ; ~
3. , TDDFT . ,
,
MLCT -
?
(
4. , TDDFT
).
?


. 29.1, .
. 29.1, MLCT

.
, . . ;

.

359
 .

. -
-

- ,

,
. , -
, -
. ,
, , (
. 29.1.
),
(
.
Qi):
1
- ; -
n1 .

.

()
(. . 6). ,
( . 29.1 -

). ,
. . ,
. - '/n =I,I x)e-i,I/n(. 1,
, .

,
1 .) - .
.

1 xv>:
:
.
, e-iii'/h 1 ) = ( 1 - i t / Ii - ;! 2
(
2
/ n2 + '" ]1 ) =
:

. ,

= (1- iEvt / 1i - ;! EJt
2
/ 2 + ... J ) = 1

, -
= e- iEvl / n 1 XV>.
, .

-,
. I,I .)-t/n( 1) = e-ivl/n 1Xv>,
,
. ,
.
,
. ,
, .
)l . ,
, - , ,

360 361


:
2:1 (XJ,v 1i,1.) 12 ( - (EJ,v - i,1. =
v
(29.1)

'1'", '1'"', , ' - ,

= 1
21cI ei(E-;,)t/n(i,1. (~I XJ)e-it,vt/h(J,v ,} i,1.)dt =
f ; V- l..~f ei(E-)t/h(' , e-it/h ' )dt =
=
1, . 2n -<> 1, I,
,
1 .
,
, ,
f
~
= -2 _ e,(E-;,)t/n(,1,1. 1 1,1. (tdt , (29.4)
, ,
(29.1).
-
-
.
Ka-
:
(i,1. 1 i,1.(t
. , e-if/h
I i,1.) ( )
w=
n
2 1('1'"'etlVI ' et) ('1'"' vih I'1'" Vih) 12 (5 (' - ), (29.2)
.
m . 26 ( (26.4.
'l'"vih, 'I'"~ih -

:
. ~
,

'l'"vih = i,1., .
j
(29.3)
'I'"~ih = J,V' ,
j (,
,
. ) .

(. 29.1, ),
. ,
,


~. - ,
'l'"iXi, 'l'"J . . 29.2
, ,
'1'"/ ,
.

5i,1. ( ) = 42(/n)

3ch ~ 2"'1(
'7 XJ,v 1i,1. )12 (5( - (EJ,v - i,1.' (. . 29.1, ),

- ( )
.

(5() = -21
_
j eiEt/tzdt, , .

363
362
 . 29.2. ,
,

:

< I > = { (_OQ2 /2)[1 - ( -irot)] - irot / 2}. (29.5)

( ) -_ 46n 2
2
I0- , - 1
5 2 n

.
(29.4)
] eXP[i(E- )-J{-Sj[l-(-iroj t)]}ctt. (29.6)
J
. ,
(29.4) , ,
.
, (. . 29.1, ).
,
.
, ; ,
oQj .
(. . 29.1, ). ,
.

,

.
- : . 29.3
C 6 H s -=-=.
TDDF 34482 CM- 1,

1
2,5
Sj =~[ M~roj )<OQj)2. 2,0

1,5
oQj
, , 1,0
*:
0,5

oQj = (1/5,8065)'L(Lql)ji(roj)-1/2 01j . 0'--_-

i
50 45 40 35 30
vl0- , - 1
* Myers . ., Mathies R.A. / / Biological Applications of Raman Spectroscopy / ed.
l. G. Spiro. - 1987. - . 2. - . 1. . 29.3.

364 365
 1 . 29.5.
2,5

2,0

1,5
1,0

r 0,5

18 22 26
E.lQ-, - 1
,
530 CM- 1. ,
. 29.4. r(N)sN
550 - 1
( = 93 CM- 1)
= 19500 - 1 --.
450 - 1 .
-- 35200 CM- 1,
- 34600 - 1 , .
.
,
,
,
, 2000 CM- 1 , ,
,

, ~
, -

2000 1
- (. 29.1). (. 29.5).


(N)5N (. 29.4). v = v = 1

: = 19500 - 1 ,
(
) 400
0"0 .... 1 ( L
) 81t 4L
4

(1,6), 530 (2,6), 1500 (0,26), 1900 (0,8) CM- 1; = 93 CM- 1. 9tz 6c4
-
II exp[i(EL - ) _] sl/2[exp(-iro/)-I]
29.1
eXP{-Sj [l-exp( -irojt) ]}dtl2 .
(0);) (~;) j

,
(J)j, - 1 ; (J)j, - 1 ; ,
.
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

366 367
 O)k, , n lnF
muu , -10
- nmuu. -12
, Ck
,
-14
-16 1
k nr - F = -18
.2

= k'P' vib I' vib) (29.2). 4
:
-20
, -22~--~--~--~----~--~

10 12 14 16 18 20
.

. 29.6. (29.5)-

(29.8) -
:

. - :

+Y[ro.AE~Y[l+ ?1',.( =: )"''-']]

=
l -31,3537 + 1,01281nknr; 1 -
[Re(4,4'-R2-)()1]; 2, 3 - [Ru(tpm)(4,4'-R2 -bpy)(py)]2+
k", = 298 (2), 77 (3) ; 4 - [()+, [(h)]2+
( = Ru,Os) ( - 2,2'-; - ; tpm - mu-(l--
[ -!(1i )] ); phen - 1,10-)

( -l tM )t(ICkI2 k/21i ) = Ft(ICkI2 k/(21i). (29.7)

,

ln knr = ln F + const.
(29.8) (. 29.6)
.

2
= [
! (
2 )][ 2 1i j(2 )]l-m/,
(29.9)

+ IQm/ =1. (29.10) 1. (29.5)

m : t<.Q = 2,0, ) =
= 500 CM- 1.
k , - 2.
,
- , (. . 29.1).
( , 3.
); -
; ; -
i-ro
t<.Q2 ]t<.Q
[---2- (1- cos O)t)(l- cos O)t) .fi.
.
(29.5) . 1.
(29.7), (29.8), (29.10) 4. (29.6) ,
. . , ?

368
 ,


L(Fl1v - /;0l1v )UVi == 0(11 =1,2, ... , ). ()
=1

1 (), , i ,
fi , U
, :
("
L(~V - f0!lv)Uv == 0(11 =1,2, ... , ).
=\

.
(. . 6):
F ,
(l) <P11

U. , uu+ == 1 ('Jf = L <!'!'),

(.. ), 2

(2)
F == LLa:F!,v~;
!,=1 =\
LIq,1
!,=1
== 1.

(l) F .
. (!) all , ,
U , () all
. , , ,
2
.
, ,
, 'Jf (~Ia!ll == 1).
. m ,
:
,
.

LLa:F!lvav
, , . 11=1 =1 (4)
; F- --

, . La: al1
11=1
, (
). 'Jf.
(2), f F :
: F al1 .
*
Fu=Uf. ~ : a
ll
, -
l1i-ro ,
):
. *
(11 == 1, 2, ... , , (4) a ll -

,
(U)I1; ::: LPP.PVi ::: (Uf)!li == LUv.kfki == LUv.kfki = Ul1i /;.
~ ~ ~

L ~y; == /;Ul1i (11 == 1,2, ... , ).

=1

371
370

2
( ~ ~vav )! )
"-l
- = (f ~v=1
- F'bp.V)Gv = .

v 1 ,

( (f F)!v - F'b)!v Ja
=1
v :::: , ().l :::: 1, 2, ... , ), (5)
. 14, 15, 17, 18
.
l
F , ,
, (3) , -
~ U,
F (
MaTp~ F. , ). ,
CMOTpeH~e -::: F http://www.webbook.nist.gov/chemistry/ (
F - ). ,
. (5) ~ , Computational
' F Chemistry Comparison and Benchmarks Database).
( - 1) ' .
.
:
. . , ~ ; ,
. , , ,
, ;
. .
(3). (
, (5) , ) . l. ,
(4),

.

: R(C-H) -
2: 2:a;F)!v av - 2: ;)!, (6)
1'=1 =1 )!=1 0,0026 (RHF), 0,0017 (2), 0,0013 (ELYP); R(C-F) -
F - . 0,0029 (RHF), 0,0010 (2), 0,0032 (ELYP);
, (6) -- - 0,41" (RHF), 0,58" (2), 0,73" (ELYP).
,
l

--

--,
R(-), R(C-F),

. . (3).
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

373
 u 2
. l

--,
,
R(-), R(C-F),

3L 3-21G 0,1096 0,1418 108,6 2

RF B3LYP
3L 6-31G 0,1093 0,1434 110,1 2,031
3-21G 2,340 1,879
3L 6-311G 0,1088 0,1442 110,6
6-31G 2,653 2,229 -
r:yp 6-31G(d) 0,1096 0,1383 109,3
1,990 1,715 1,882
" 6-31G(d)
L 6-31G(d,p) 0,1096 0,1384 109,2
6-31G(d,p) 1,981 1,704 1,821
3L 6-31 +G(d) 0,1094 0,1399 110,4
6-31+G(d,p) 2,191 2,092 2,170
3L 110,3 0,1092 0,1396 110,3
6-311 +G(d,p) 2,068 1,884 -
2 3-21G 0,1093 0,1428 109,1
2,023 1,717 1,786
cc-vDZ
2 6-31G 0,1094 0,1454 110,7
2 6-311G 0,1089 0,1456 111,1
2 6-31G(d) 0,1092 0,1392 109,8
u
2 6-31G(d,p) 0,1088 0,1390 109,7

2 6-31+G(d) 0,1087 0,1405 110,7
( 298,15 )
2 110,3 0,1091 0,1389 110,2

-
2 cc-vDZ 0,1102 0,1383 109,3 ,
, /
/
2 cc-vZ 0,1087 0,1379 109,8
6-31G +325,6 1 125
2 cc-vQZ 0,1085 0,1382 110,0 RP
6-311 +G(d,p) +227,6 1223
2 aug--vDZ 0,1084 0,1409 110,6 RP
6-31G +27,8 1423
2 aug--vZ 0,1087 0,1388 110,2 2
6-311 +G(d,p) -153,0 1603
0,1106 0,1385 110,0 2
6-31G -184,7 1635
3L
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simons. hec. utah.edu/TheoryPage 1. ............................... 5
2. ...................................... 12
2.1. ................................................ 12
2.2. ...................................................................... 13
2.3. ................................................................................... 15
2.4.
.................................................................................. 19
2.5.
............................................................... 22
3. ................................................ 29
3.1. ............................................... 29
3.2. .......................... 32
4. .............................. 34
4.1. .............................................................. 34
4.2. ........................................................... 36
5. .................................................................. 40
6.
...................................................................................................... 54
7. ...................................................... 64
7.1. ................................. 64
7.2.
.................................................... 66
7.3. .......................................................................... 68
7.4. ......................... 69
7.5. ................................................................... 73
~2
7.6. J ................... 75
7.7. . .............................. 76
7.8.
. - ....................... 81
8. . ........................... 84
9. .............................. 92
10. ....................................... 111
11. ............................................ 121
11.1. ......................................... 121

381
 11.2. ........................................................................... 122 18. ................................................ 250
11.3. ...................... 124 18.1. ........................................................... 250
11.4. . 18.2. - ..................................................... 256
........................................... 128 18.3.
11.5. - ................................................... 136 ............................................................................... 259
11.6. ......................... 137 19. ....................................................... 263
19.1. ........................................................... 263
J' . 19.2. NDO ................................................................ 265
19.3. CNDO .......................................................................... 266
12. ........................ 141 19.4. INDO ........................................................................... 268
12.1. 19.5. MINDO/3 ..................................................................... 269
.................................................... 141 19.6. MNDO ............................... 269
12.2. ................................. 149 19.7. INDO .............. 274
13. 19.8. ............................................. 274
~~~~~~~i~~~~~~ ............................... 153 20. ....................................................... 276
20.1. - .................................................... 276
14.1. :: ~ ........... 161
........................................................... 161 20.2. - .................................................... 282
14.2. ........................................... 162 20.3. ............................................ 285
14.3. - 21. -. .................. 289
( ) ...................................................... 164
14.4. ................................................................ 168 .
14.5. -

14.6. ~~:~::~~~~~~;~~~~~~~~~~ ............. 171
22. ..................................... 297
........................................................ 172 23. m ...................................... 302
14.7. - ............................... 173 23.1. ....................... 302
14.8. -
23.2. ......................... 305
......................................................... 174 23.3.
14.9. - S2 ................................... 178 ........................................................................... 310
14.10. ................................................................ 184 24.
:~. - ........................... 188 .................................................................................. 315
.1. ........................................................... 188 24.1. .......................................... 315
~~.~. ~eTO ........................................... 188 24.2. ................................ 325
.. ........................................................................... 190 25. ................................................ 327
15.4. ........................................................ . 193 25.1.
15.5. ................................ ::::::.:: 200 ............................................................................ 327
16. . ............................. 208 25.2.
16.1. ................................... 208 ............................................................................ 329
16.2. , ..... 213 26. ...................................... 336
17. , .................. 226 27. ............................................................................ 344
17.1. ............................................. ..... 226 28.
17.2. ............... ::::::::: 231 .............................................. 353
17.3. 29. .......................................... 359

17.4. ~~~~.~~~;~~.~~~~.~~~;~.. ~~ .................................................... 237 ............................................................................................... 370

................................................... 242 ................................................................................... 379
17.5. ....................... 246
17.6. ,
................................................................................. 248
382