535.37(075.8) : /, ISBN (075.8) ISBN , 2008, 2008
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- Nickolas Collins
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2 535.37(075.8) : /... : -, ISBN ,, -,,, -, -., «-».,,, (075.8) ,.. ISBN , 2008, 2008.,
3 , -. :,, - ;,, ; - ;, ;,. -, -,, -., -, -,, , - -,,. - -,,,,, (), -.. 3
4 1 1.1., -. - :,.. -,. -, , : -,,, - 4
5 : ; 1, 2, 3.,,,,,. -. -, ij = h ij = h/ ij, ij, i- j-; h ; ij ; ij ;.. - (1 = 1 1 ). ( = 2). : -, (1 = 10 6 ), (1 = 10 9 ). (1Å = ). ~ = 1/, ( 1 )., -, -...,,. E i E j. -. ij n10 m () - : ij 0,1 10., - (), (). - (- ), -, ().. () () - 5
6 , : ( r,, ) = R r = R r,, (1.1) R(r),,. n, l, m. - R r = f 1 (n,l), = f 2 (l,m), : = f 3 (m). n = 1, 2, 3, - ( n ~ n 2 ). () ( ) l( l 1), : l = 0, 1, 2,, (n 1)., -, : s, p, d, f. (). m - z ( M z m ), m = 0, 1,. l. r p, r p. - ( ), -,. m (m = 0), (m = 1), (m = 2),.. m s, m s - l,. 2 2 S s( s 1), s l,, s = ½. z S z m s, m s, m s = ½., ( r,, ) R r, S s. (1.2) 6
7 , n, l, m, m s., n, l, m, m s n ', l ', m ', m ' s., : m = m m ' = 1, 0. (1.3) -. L S, -, - J. - - : J = 0, 1 J 0. (1.4), S = , -,.. - m, z, -, m. -, n.,., -. z,. -. z. -, -. ( ). - 7
8 ,,., E v r : E = E e +E v +E r. (1.5) - : >> E v >> r. (2.8) E v, r. - ( ) --,. E r : ; ; E r ; v evr, - ; v vr, - ; v r, 8
9 , -,, ij 0,025 0,5., - - -, - (- )., -, 10 5, ( -), -., L S L,., - = 0, 1, 2, 3,, :,,,. -,,,. S, - (g = 2S + l),.., S = 0, S = 1 p.,..,., -,, (+)., ( ). (g), - (L) (0, 2, 4, ), (u) L (1, 3, 5, )., -,, (+ g) ( ). () - ( g) (+ u). 9
10 (+) ( ). g., -, g, u. - : = 0, 1; S = 0; ; + +; u g.,. -. -,, - :, ; *, *., -, -.,, -, : g, u, u, g, g, u ; u, g. - (ls) 2 (1S*) 2 (2s) 2 (2s*) 2 (2p) 2 (2p) 4 (2p * ) 2. - D, h, - (l g ) 2 (1 u ) 2 (2 g ) 2 (2 u ) 2 (3 g ) 2 (1 u ) 4 (1 g ) 2.. ( 2 ), D h, 1s-. : -, g, u : u; g., -,. 10
11 2,,, g u : 2 2 -, yz, a xz: g ; u ; , -,, , - 0 (. 1.3). - -., 10 16, v ,,, -. -, - g. () 11 u.
12 -,,, : q dr r r. (1.6) r r - r, - -., ,, -. U(r) - r. r -. r -,, -, r., -. U(r) : 0, 1, 2, 3 r 12
13 , () ( ).,,, -, -. (. 1.3) () -.,. -, 0,. - = 0. ( ) - r e., ( ) ( ). -. : 1.,,, ,, -,,,,, *, *. 3.,. 4., -. 5., -. 13
14 -. -.,.,., -., -.., -,, -, K (r) = U K (r)e ikr, (1.7) U K (r) = U K (r + ), - c, ; k -. k k = 2 1, k.. -,, -, -., :
15 2., -. 3., ( ). - - (. 1.4)., ( ) ( ). 4. Eg,., -. -, -. 5., -. -,. -,., -. (, NaCl, MgF 2.), -,,, = k. (k),. (k),.. (k + g) = (k) = ( k). k (,, z ),, -, = k. 7.,,,, -. ( ) - N, - N., 15
16 N ( ), k.. - g- 2gN. N,., ,. 8., -,,, ,.,,. N (), :, -.,., -,, ( ).,. -,, ( ), -., -,. -,,. ( ), -., 16
17 , g : ; 1, 2, 3 ;,,, ,, , ().,., ,,. - -,, 3 3s, r
18 ,,,. 3s-Na 3p-Cl 3s-Cl 2p-Na 3s-Na 3p-Cl 2s-Na Na + Cl Na NCl,, m e., - (),.. (), - (), (v), (k) ( m ) : e 2 2m e 2 k 2m 2 e, V Ek 1, k 18 m 2 k 2. (1.8) E( k),,, -, V = d/dk. -. -,,,. -, -,,, m > p m. (k),, -. k- e
19 ,,. (k) - () k,.,, g 1, g 2, g 3. a i - : g 1 = 2[a 2 a 3 ]/a 1 [a 2 a 3 ], g 2 = 2[a 3 a 1 ]/a 1 [a 2 a 3 ], g 3 = 2[a 1 a 2 ]/a 1 [a 2 a 3 ],. = a 1 [a 2 a 3 ], = g 1 [g 2 g 3 ] = (2) 3 /., () V k- k : V (k) = 3. (1.9) 2, - k,. -,,, k. (k) - () k. -..., (k), - 19
20 ., - (k),. k,,, k-, ,. 1.6,.,, L.. - k = 0, - -, L-. [100] 0, [111] 0 k L., (k), NaCl,. 1.7,. - - ( ) %. -,., (.. 1.5) , j + = 3/ j + = 1/2. (j + = 3/2)
21 k., (k). - : ns - ( )., 0,66 0,28 0,8 k = NaCl () (). N1 CsCl s-.,, s-. s- d d- ( 12 ' 25 ). (k) -, - (k) [111] k [100]
22 .1.7,. (k) - - [111]... (). k = 0, , k = ,. E 2 1 k [111] [000] [100] (1) (2), (.,, 1.2).., -, (). ( + de) dz ( ). - 22
23 f(). dn : dn = f()dz. N() -. dz N ( E) 1.10) de dn = f(e)n(e)de., - 1 2, 2 n f(e)n(e)de. (1.11) 1 N(E), -,.. f(). -,, : f(e) = F kt 1, (1.12) 1 k ; ; F,.., (1.12),,, -, 0,5..,, [14], -, -. 23
24 :, - -,, E - :,,, ; : n = dn/dt, c 1 ; : n = d n /ds, 2 1 ; : F n = dn/ds, 2 ; : = d/dt, ; : = d/ds, 2 ; : F n = d/ds, 2 ; (), (), (/ 2 ) (/ 2 )., -, : -, -,.,. de -, dv, dm : D de dm. (1.13) (): 1 = 1 /. 1 = 100 / : 1 = 10 3, 1 = , (/), (/). - (/ 3, / 3 ). - : 1 = 1 / = 100 = 6, /. 24
25 (P) - dd dt P = dd/dt. P -,, /(). P (/), -, /(). : 1 / = 1 /() = 1 / = 100 / = 10 4 / = 6, /(). : D, ; P, /. -, -. -, , ( ).,,. - - (, ).,. -,. - -, (.. 1.9) -., -,. 25
26 ,, 0 m : 4mM 2 E cp E0 sin / 2, (1.14) 2 ( m M ).,, ( - ) (< 5 10 ), ,. -, -.,,.,,,. () 0 ( ) , - - 1,5 4 - (< ) , -, ( - 26
27 ) ( ), , (),... - (> 1 )..,, - -,.,,,. de/d. -, : ( de/d) = ( de/d) + ( de/d). (1.15) - : S = de/dl = ( de/d) (1/)S = (1/) ( de/d), (1.16)., -,, [34]. N 0 Z, N 0, Z.,,,
28 L 1 L 6 - ( ). 1, 2,., -. :.,. 1.9, ( ). -. d, - - ( ). l 4 l 3 e - l 1 l 1 l 5 l 2 l 6 C 1 C 2 A x , ( ). -, ( - ) R 0, E 0 0 ( E0) de S( E) 0 R, (1.17) E 0 ; S(E) -. R 0-28
29 . - d. - R 0 / d, Z E 0 R 0 / d. (1/)S (1/) = (1/)d 2 / dl., (1/) - 2, d, dl -,. -,..,, ,,,. -.,, ( ), (. 1.10, ) - (. 1.10, ). - (),,, 29
30 ,. - ( - ) R ex, R mx () ()
31 , -. -, -,,, -,,.,.,, -, -. - R ex = 0,53E 0 0,106, 2., - : D de. (1.18) dm : D 0, D max, R ex R max. D max = 1,6 D 0. R m = R max /3, - R 0 2 R m D ,,., -,, -,,,,.,, - 31
32 ,, -, ( ) de/dx (1 8 ) (10 15 %)., , ~ 1/3 R ex, ~ 2/3 R ex. -,. -, -. 4,5x D ( x) 0,5D 1 sin 0, 2 max. (1.19) R ex 32
33 , -, , ; -, -,. -, -.,, - -, ( ). 1.3.,, -, -, (), -. -, - (.. 2). -,, -. -,, -, , 10 15, -,, 0,. 33
34 ,,, , -, - n(e) (E),. n(e) (E), ,..,.. [5], - NaCl , n(e), , «-» -.,,. ()
35 -. -, , ( - ) , [4]: (m e m h );.,,,, ; E 0 ; ; I e 2 I e 1,, ; E g I I , (1.20) 35
36 I I 1 ; 2, ; ; 1 -, ; 2 < 0., ,. -., -.,. l e 1/l e = 1/l eo + 1/l ea, e = l e /v e, v e ; l eo ; l ea -.., NaCl < 2,. t = N. e, N., - 0, 0. -,, -,. -, (. 1.15). - - ( ). - 36
37 .. -,. -. KBr, RbBr, KCl RbCl [8] (, - ) -, -. -,, - -, - () : ; ; (V k -) -, : D ~ 1/2 ; D ~ [exp( 0/kT) 1]., - -., -,
38 ,. (. 1.5),. (1.20) : = e E + E g. (1.21), e I 1 I e (1.21) = + +, e 1 e I 1 (E 0 ) (E 0 ), 0 = E g (1+ m * e * m m * p 2 38 I e 2 ), 0 = E g (1+ * m p * m e m * p ), (1.22) * *,. (1.22),,, - Eg, 0 0,. - (E0 Eg),.. -., - 0 0: E e- = E g + E e + E, (1.23) E e E, 0 0 0,.., -. -, - n(e) (E), * *,.. m e m p E e- = (3 4)E g,, m * p - m * e, ( v << Eg), Ee- = (1,5 2)Eg..
39 , -, -,, :,,. -. t < KBr RbBr t < KCl RbCl - (. 1.15) V k - ( - ),,. - ( v ),. v,,., , , , 2., -, , -. - ( ), -,.. V k -.,
40 ,, ( + e)-. -, -, (F-, H-). ( + e)- (, ), 2 (V k -). -.,, F-, H-.,,. - F- < 10 11, (, -, ), - V k -,.,, - (,, ) - ( ), -, - ( ).,,,. : ( ) ,,, -, V k -, F- -,,. ()., - ( ). 40
41 ,, -, ,, -,, -.,.. - : (,..) -.,, -, ,... -,, - 41
42 . : p t e t. (2.1) a a. - 0 (. 2.1, 2.2). 0 cos( t), (2.2) p. -, -,,. : 2 H E sin, (2.3) 2 r0c r 0 ( ); E H S,, - z. a () S( ) = (c/4)(e H) 4 S( ) 2 4 r c sin. (2.4)
43 (2.4) -, , -. (2.4) -,, 1 : S. (2.5) 3 3 3c : ;, - -, / 2., : = S( ) (2 sin ) r c S. (2.6) 3 3 3c ,,. - 1: s.,,,,, -
44 . E - ( ). ( ) : ; ,. = h, hk ( k ; h ). 1-2 = 1 h., -.. -, -,,,,.,, -, -,. - 44
45 , -,, () (), >>. - (/) 2 - n (n + 1). -, , / , -.,,, -,.,. - -, / 1/ , , -. - n (/) 2(n 1).,,, - ( (/) 2(n 1) ). -.,,,. -,. m n -, : mn R 2 m 45 n 2, (2.7) ( ); m n, () -
46 m n. -,... - m n, -, -. R mn = 0,. R mn,, m n. m n, R mn 0.,,. 2.2.?.., -,,,.? -.,. -, - : N * /N 0 = g * /g 0 exp( E/kT), (2.8) N * N 0 ; g * g 0 - ; ; k ;,. - I ~ N *.,.,..,, - -, -. : I = 2,3I 0 lc, (2.9) I 0 ; - ; - ; l ; c - 46
47 . (. ), -,. -..,, -,,., -, -,,. -,. -, (-,,.), (10 9 ),. -, (.,, [9], [10], [11]). : (), -,,,,. -. :, - ; ; - (-, -, -),, ;, ;, ; 47
48 ,, - ;, - ;, (,,..) -,. -, -,.. -. () - -.,,, -., -. - :, -,,, - ; -;, -. -, (. 1.3), -.,
49 ,. -.,, -,,. -,,, -.,.,,, -., -,,. -, : 10 9 > :,, : (), (), (). : ; E i, ; () -,.. 49
50 , ,., 1 2, , , -,. - : - ; ;..,, -,. - () -. -, ( - ),, -,.,.,, - 50
51 ,,,, :, -, ( - ),,,, -.,, :, - ( ),.., I.,,, (- ) / 2. -.,.,, -. -, -, N, - - : I ~ (dn/dt). (2.10) (), - : I = h mn A mn N m, (2.11) N m m, n ; h mn m n; A mn, -,.. 1 (- 51
52 ). :. A mn = (64 4 /3h 3 ) 3 mn 52 mn 2 R. (2.12), - mn -..,. I = f(h), I = f(), I = f()., ( - )., ,. - (,,,.),.. - = h., -,. -.,,, ( )., -,,,.. -,. - -.,.,, l, :
53 lc I = I 0 1 I = I 0 10, (2.13) I 0 ; I - l; k -, k = 0, k (, ) -. (, ): T = I/I 0 = 53 lc lc 10 ; (2.14) D = lgt = lg(i 0 /I) = k l; (2.15), D = lg(1/t )100 % = 2 lgt (%). (2.16) -,,. ( ), ( - ). k, : (k ),. -.,,,,. -. -,, -..,
54 ,,, - ( )...,.. - (). -. : - :.,, : h = h + Q, h ; h ; Q,.,. 2.5,., -, -., () (),..,. 2.5,.,, ,
55 2,, , ,, ,,..,. :,. D * (), () -,
56 . -, ( ), ( ): = /. (2.17), -. - (N ) - (N ), : = N /N. (2.18) = Nh, : = / = N h /N h = ( / ). (2.19). - - (., -,. 1.3). ~ ,.. -.,, -, -. -., -, -.,.,, -,, - D = f() I/v = f(),, - v 0 (. 2.6, ). (v + v ) = 2v 0, v v v 0 -. v 0..,, - 56
57 , -., [9]., : 1 6; 2 ; 3 ; 4 - -, (- )., -,,, -, : hv = hv + E r, (2.20) E r. - I(t). - 57,
58 ,.. -. :., -, (. 1.3), -,.. «-» [7], , ,,. 1, ,8 I, P 0,6 0, ,2 0-0, t, : 1 ; 3, , -. - () () - 58
59 ., -. -., t = 0.,,. N ; N t;. dt dn = Ndt. (2.21) ( t = 0, N = N 0 ), N = N 0 e t. (2.22),,,, (2.11), I = Nh = N 0 he t = I 0 e t, (2.23) I 0 = N 0 h t = 0., -.,, = 1/, I = I 0 e t/, (2.24), (2.24),, -., -., I(t) = I 0 e t/. t 59 t t ti dt / I dt (2.25) 0 0
60 ( ) -,..,, -,.,. - - I 0i i : I t = i I 0i ( t/ i ). (2.26) () - ( R ) ( 0 ). = R : = 1/ = 1/( R + 0 ). (2.27) - (- ) N = N = N 0. k - ( ), - : 2 dn = k N N dt = k N 0 dt. (2.28) (2.30) - : N = N 0 /(N 0 k t + 1), (2.29) : I (t) = dn/dt = N 2 0 k /(k t N 0 + 1) 2 = I 0 /(1 + t) 2. (2.30), -,. I 0 = N 2 0 k, - N 0 - I, I 0 -, I 0 I 2. 60
61 , -, : I(t) = I 0 /(1 + t) b, (2.31) b : 1 b , -,,,. - () ()., - () (), -. (2.28) N ( N ) dn = k N dt, (2.31) N = N 0 e k N t, (2.32) N. - : I (t) = dn/dt = N 0 k( kt) = I 0 ( t/). (2.33),, - -,., - ( ), N >> N.,, -, -,..., -, -, -,...,,. 61
62 - I 0 (). (2.33) I 0 = N 0 k, = 1/k,... - I (N 0 I ), I I 2, I., -, I 0 I : I 0 ~ I 2, ~ 1/ I. (2.34) -., - (). : -,,,,.., 0 1.., ( - ),. -.,.., -, ,, ().. 62
63 ., ,, -,, -. «-» 0. = 0 [ ( 0 )], (2.35) 0 - ;. : -, -. -, -.. -, -. ( ), ( ) , -. -., 63
64 : / n = 1+n, (2.36) n - ; ; n. -, , , ( - ) I 0, S = I 0., -.,.,,,.. 2.9, I, (. 2.9, ).. 1, II., 64
65 II., - -.,.. -. II 2 2 I II III I 1 1 II I 2 r r r. 2.9., [11]: ) ; ) ; ) ; I, II, III,. 2.9, II - III, 2.,, II. 2 II III, , I II., -. - (- 2 ), 1 2 I, -. -.,, - 65
66 .., (), :. -, -,,, ( ). R -,, 0, - I : I pr, (2.37) I p 0 R p 0. ( R + 0 ) - ; I 0,.. -, = R.,,, ,. -.,,.. : 0 = 0 exp( E/kT); (2.38) = R + 0 = 1/ R + 1/ 0 = 1/; 0 = 1/ 0 ; R = 1/ R, (2.39) R (- - ); k ; 0 - ( ); E, -, (. 2.9). 66
67 -,. 2.9, - : 1. (2.40) / exp E kt R 1 R 0 / () I(), : () = [1/ R + 0 exp( E/kT)] 1 ; (2.41) I() = I 0 ()/ R = I 0 [1 + R 0 exp( E/kT)] 1. (2.42) - () I() (2.42), I(). -,. I 0 () (- ). S = I 0 () () (2.43). - I(), -, ()., - I 0 () () -, , -., -. -, -, ()., - ( )
68 -,,, ,,., I,, -, ( h) - ( )., -,,, k,, ,, , [24].,.,,, -, : -.., : ; - ; ; «-» ;. -, : - ; - ; ; «-» ; 68
69 (,, ); - - (, -, ).,,,,, () : (D ; D* ; ; * ; h ; h ) [24] 69
70 ,, : - (,,, ).,,, -, -., -. -,. I, , [24],,,, -., - -., 70
71 . :,.,,, - -.,, v evr = v e + v v + v r., ,. -, (. 2.12).,, : (, h ); () I ; ( h). - -, : ;
72 ., ,,, - (.. 2.4).. [11], ,,,, -., S = ½ ½ = 0, - g = 2S + 1 = 1,.. S 0.,, ( ) -. S 1 (. 2.14),.. -. ( ) - S = ½ + ½ = 1, g = 2S + 1 = 3,.. - (). - : +1, 0, 1..,., :., - S 2, 2. S -., - : 72
73 - (S S) - ( ) S , S (S O) S 0, ( ). 1 -., - S 1 S 0, -,. - ( )., (r = 0) - 1,,,,. r 3,, S 1.. ( - ) S 1 S 0. 1, 1 ~~ S 1, - = ST : N 1 = N1 ( ST /), (2.44) ST S k : 73
74 k = k TS ( ST /), (2.45) k TS 1 ~~S 1., - -.,, ,,. -,, -,., -, : - (S ~~~ S) ( ~~~ ) ,.. - (S ~~~, ~~~ S) , S 1 ~~ 1., - S 1 1,.. - ( ) S 1, (r = 0) S 1 1,, - 74
75 ., 1 (r = 0), -., -. 1 ~~ S 0,, S 1 ~~ ,, 1 S 0 S S 0, -., -,.. -., S 1 T 1 S 0, r [11],, -, -, - 75
76 - : h 0 + S 0 S 1 ; S 1 ~~ S 0 + ; S 1 ~~ 1 + ; 1 ~~ S 0 + ; 1 S 0 + h ; S 1 S 0 + h ; 1 + ~~ S 1 S 0 + h., S o., -,. E 1 - ~10 15 S 1., ( r = 1, 2, 3,..) S : S 0 ; S 1 S 2 ; 1 ; ; ~~ ; E 1 E 2 [9] 76
77 S 1 (r = 0). - 2, S 2. ~ ,, -,,, S 1. S 1 S ,. S 1 S 0, - -., 1. - S , -, - 1. (, ) - 1 S , -., ( ) :..,,., 77
78 . -, -., -, -. - [10, 12, 16]. - -,,.. -. Ne, Ar, Kr, Xe. -.,.,, 1.3.,,. -,,., -, - ( ), -,, , - (k e = k p )., -,.. k = 0 (.. 1.7)., - 78
79 -. -,, -. I(h) : I(h) = B(h E g ) 1/2, (2.46)., - -, -., - hv > Eg.,, -,.., (. 2.16)..,, -, -, : I(h) = B(h E g + ) 2, (2.46)., ,., (). -,.. ( ) 79
80 ( ) l kl > 1 (k ), - : I = k l I /(1 k l ), (2.46) I , ,, -,,. -,, -,,.. -. ;,,,. 8 h, , : 2 ; 1 2 [28]
81 -,..,.. -, -., -.,, k = 0, -, k, ( ), , -, [10],., 81
82 -, -, :, -.,, -, -,. - -,.. -.,, ( )., -.,.. h g h k k : ; h h k k : ;, - (. 2.18, ), 82
83 hv = E g E, (2.47) E , - -, -. (. 2.18, ),, - E. hv = E g E E. (2.48) - - (. 2.19), -, , 2, 3, 4 5,, 0, 1, LO, , ,7 1,0 1,4, h InP 6 [28] 83
84 , k 0 <, ,,. -,.. -., -, , ( ). - -,., -, l R. l/r >> 1, -, -. l/r << 1 (- ).. -..,, - ( ) , 84
85 ( - ) ,,. -, -. -.,, -,.,. -,. -,, -,, -. -,, -. V k -. V k - X 2 ( , ). - ( ). + 2 V k, %. - 2, ( V ), - 85
86 . V,,., (- ) 0,1 2,3. 2 < KBr RbBr < KCl RbCl., 60 0, : on-; off- - - V k -. V k -, -,, : on- off-, - ( 2,.. V k -) (. 2.21). on- V k -, off- - 2 <110>. 2., - on- (D 2h -), : 1 u 3 u..,. - 86
87 : (-); - (-); u 1 + g ( S o ), - 3 u 1 u - (. 2.22)., c. S 1 ( 3 u 1 + u ) [1] 87
88 - -,.. (2 10) g + (S o ) ,.., -. 1, - -,. -, -. -, 3 u 1 u (- ) , u 1 g ( ), -, - - ( 8 40 )., NaJ., I, ,5 5,0 5,0 4,5 4,0 3,5 3,0 h, (1) (2) NaJ = 0,
89 , - -, - on-, - off-. - -, ( ). -, on- -, off- -, - ( ). -, -., NaJ < 5, - 4, «-»., -,,. -,,. -,., ()., -, ; -,. -.,. 2.24, - 89
90 .,,, ,. D ( ) - - (. 2.25) - -., , ( 2), - ( 3). A C V D 2 C C 1 h ,,. - ( 3). hv = E g E, (2.49) V hv = E g E E, (2.50) 90 1 h A 3 2 V
91 ;, ( ),. -, -,.., F- V k : ; ; (1) (2) - - -, -. d,,, -. -, 91 Q 2 1 Q
92 = 2 /r., - (. 2.27), hv = E g d + 2 /r, (2.50) r. D r h (, ), -., (r < 40 Å).,,. E C E V Si-S Si-T 2,20 2,25 2,30 E, GaP 1,6, - Si-S Si- [28] - da - r: da = P 0 exp( 2r/a da ), (2.51) 92
93 P 0, r; da. -, - r, r. - - c N da - I = const r 4 ( 3 4 Nda r 3 ) ( 2r/ da ). (2.52) -, -., - - -, : , - - c,..,.., (2.52), ( r) hv , -, -.,,..,,,. -, 93
94 . -..,. - - (). -. : ; - ; ;, - ( ); ; : Tl +, In +, Ga +, Sn 2+, Pb 2+.., Ag + Mn 2+,., -,. - : F, F 2, R., ( NaCl),, -, I., -,,, Z 1 -.,, U-. -.,,, -, II., -. Sn 2+. Z 4 -, - 94
95 ( 2+ ),. F A - F-, -., - NaCl, (U 2 -), - (U 1 -), (-).,, ; -,. -,,, F-, F F 2 - F F-, -,, R-.. - I 1 1. F- -. F'-,.. F-, ,. I (6s) 2 1 S 0. - (6s) 1 (6) 1 3 0, 3 1, 3 P 2 1 P (O h ) h, : 1 S 0 1 1g ; F 1u ; 1 P 1 1 F 1u ; u ; E u, 3 F 2u. 95
96 -, -, - D- - : - 1 1g 3 F 1u 5,02 ; - 1 1g 3 E u, 3 F 2u 5,96 ; - 1 1g 1 F 1u 6,35 ; D- F 1u 1 + 7,2 ; - 3 F 1u 1 1g 4,06 ; - 1 F 1u 1 1g 5, , - 5,02 4,06,. 5,0 4,0, ,, - Q.. Q Q Q Q
97 -,, - (. 2.30) , -. : ( ). 2., () , -.,,,. -. -, - : ( - ) (- - )., -,
98 , -, -., ( ), -, 0 0, 1 1, (.. 1.3). - : , 1 2, 2 3.., - -,. -,... -, ( - ) = 0, -,... -,. -, ( - ). -,. ± J ( ). - ( J ), -. -.,., -, -., 98
99 , ( ) ( ) ,, ,. -. CaF LaCl 3 r 3+. -,,. ( ) -, , - -,.,,,. - -., -, ( ),,
100 . 1 +,, I Z U II Z U 1 - U F- F F F
101 3 (. 3.1)..,, -, - 2., : 1 ; 2 (); 3 ( ); 4 (); 5 ; 6 ; 7 -, -. - ( ) , - (- ). () - 101
102 , : ,, : 30 0,5. - -, -.,, 2, D 2.,,,. -. (),.,, , -, -., -., -. -.,
103 ,, () -. «-» [7].,. -,, -, , 0,5 10, 0,5 20 ~ , ,,. (, )
104 . - : -. ( ) -., -, -. f() -,. - - (t). -, F(t). t F().. (. 3.3) () (),,, - d' = ' (')d'. ( '),..,. - () (): 104
105 y()= ( ')(')d'. - (), - () ( '). - ( '), (). F() y() -.,. -, f 1 f' : 1 () O 1 ; 2 ; 3 () O 2, - (,,, ). - () -. O 1 O 2,.. ( ). -. (- ),, -, ( ) 105
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