Документ взят из кэша поисковой машины. Адрес оригинального документа : http://www.students.chemport.ru/materials/stats/08.pdf Дата изменения: Thu Jan 15 18:05:43 2009 Дата индексирования: Mon Oct 1 20:49:04 2012 Кодировка:

- ( ) , : . : - . , . . - . N! . : E = Uo + E. . , , : . , Uo ( ), Uo . = 0 , .. = - E = - ( Uo + E,). E, - . 10 / Uo. = - Uo. ( ). 1000 /, : 20 / (4 - 10, 2 - 50). - : , -- . NaCl, : 6 R, 12 21/2 R, 3- : 8 31/2R, 4- : 6 2R ..

2N U = Nu, u - . : (1- ) : a e2 u ij = ± , + , - . e -. r ij n r ij ij = rij / R, rij - , R .

1 2 2 a 1 e2 = a 1 ± e 1 = aA n - e , u i = u ij = ± n n p ij R R n j i p n ij R j i p ij R Rn j i j i p ij R

= ±

1 , = 6/1 - 12/21/2 + 8/31/2 - 6/2 + .... - p i, j

, + . NaCl = 1,747558... An = 1/ pijn . Ro ( ) = 0 . ,

1


u = 0 na A n / R o n +1 = e 2 / R o 2 . aAn R R =R o

u=-

e 2 Ro

N e 1 1 - U o = - n Ro

2

1 1 - . n - n

10, .. ( , R ), 10%. NaCl 862, 96 / (n = 9). 6-12

z bN Uo = - 1 2R 16

6 1 - , z1 - 1- , R1 - n

, b - . . . . 3N - 6, . 3N, .. N (, ). 3N N . . . , . : -1 3N h i h i Z = exp - . .. , N ! . 1 - exp - 2kT kT i =1 lnZ V, kT2.

h h E = U o + + h i =1 2 e kT -
3N

, 1

S = E/ T + k ln(Z). . . : . 3 q = [ 2sh(hn/ 2kT)]-3. N 3N . ..

h 3N h + . 2 exp [( h / k T) - 1] h 2kT) = hn/ 2kT E = U o + 3N + 3Nk T. 2 S = 3N k ln 1 - E = U o + 3N
2 -

, , sh(hn/

g h + h h - e kT e kT -

. 1

C v = 3N k

e h . . >> 2 kT h 1 - e - kT

h kT

= hn/ k Cv 3Nk: - . h 2 h - kT T << . ( 0). C v 3N k e

kT

2


3 2.5 2 1.5 1 0.5 0 0

Cv/R

T/ 0.25 0.5 0.75 1 1.25 1.5 1.75 2

3NkT 3Nk = 3R. : , . : ( -) pvo h / kT 1 (n + 2)(n - 1)(ao / a)n + 3 - (m + 2)(m - 1)(ao / a)m + 3 = + kT exp(h / kT) - 1 2 (n - 1)(ao / a)n - (m - 1)(ao / a)m

+

mnuo uo m(ao / a)n - n(ao / a)m . (ao / a)n + 3 - (ao / a)m + 3 , u = m-n 3(m - n)kT

uo = - q , m, n - , m = 6, n = 11, ao - = 0. .. pV/ RT = f(n, ao, n, m). = 0 . . . . ( , - ) . g( ) = 4V

1 2 2 , c l, c + 3 3 ct cl

t

- . g = 0.

. , ( ). , , . , 3N ( 1/3 3N ) g( )d = 3N = , - . , 4 V 0 cl ct . QD = hn / k. = hn/ kT. = Q D/ T 3 D / T 3 3 _

h h + E = 2 0 exp (h / k T) - 1

kT g( )d = 9N k T h

x x exp (x) - 1 + 2 0

dx.

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= (9/8)NkQD x _ x3 E = E o + 9N k T x -3 dx. Uo o , exp (x) - 1 0 2- . 3 x x 3 D ( x) = dx. D(x) 1. , x 3 0 exp ( x) - 1 C V = 3N k D ( x) - x



dD ( x) dx

. CV = 3Nk, :

kT C v = 9N k h

3 D / T

e xdx x4 . (e x - 1) 0

, E - Eo = 3Rp4T4/5QD3 Cv ® 0: h 12 4 Nk 3 Cv = T , D = . k 5 3 D . () . .
3 2.5 2 1.5 1 0.5 0 0 1 2 T/ 3 Cv/R

(. ) Na 150 Cu 315 Zn 234 Al 394 Ni 375 Ge 360 Si 625 A. 157 342 316 423 427 378 647 Li 400 K 100 Be 1000 Mg 318 Ca 230 B 1250 Ga 240 As 285 Bi 120 Ar 85 In 129 Tl 96 W 310 Fe 420 Ag 215 Au 170 Cd 120 Hg 100 Gd 152 Pr 74 Pt 230 La 132 Cr 460 Mo 380 Sn() 170, () 260 C() 1860 : QD =134,5[/ (V2/3)]1/2, - . , 1- 100.

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