Volume 14, number 3 P HYS I CS L E T T E R S 1 February 1965

being of the o r d e r of 10 -4 . 2. Christenson, Cronin, Fitch and Turlay, Phys.Rev.

The m u m e r i c a l , r e s u l t quoted above can only
be r e g a r d e d as p r o v i s i o n a l in view of the ap-
p r o x i m a t i o n s made in the calculation. H o w e v e r ,
the e n h a n c e m e n t f a c t o r R is c l e a r l y of the o r d e r
100. As we pointed out above this m e a n s that
c u r r e n t e x p e r i m e n t s on the e l e c t r i c dipole m o -
m e n t of the c a e s i u m atom can be i n t e r p r e t e d to
y i e l d a l i m i t on the e l e c t r i c dipole m o m e n t of the
f r e e e l e c t r o n many o r d e r s of magnitude l o w e r
than that p r e v i o u s l y a v a i l a b l e . A m o r e c o m p l e t e
c a l c u l a t i o n will be r e p o r t e d in a f o r t h c o m i n g
paper.
References
1. L. Landay, Nucl.Phys. 3 (195~ 127.
Letters 13 (1964) 138.
3. R.A.Carhart, Phys.Rev. 132 (1963) 2337.
4. Smith, Purcell and Ramsey, Phys.Rev. 108 (1953)
120.
5. N.T. Meister and T. K. Radha, Phys. Rev. 135
(1964) B769.
6. J. Goldenberg and Y.Torizuka, Phys. Rev. 129
(1963) 2580.
7. L.I.Schiff, Phys.Rev. 132 (1963) 2580.
8. P.G.H. Sandars and E. Lipworth, Phys.Rev. Letters
13 (1964) 718.
9. E.E.Salpeter, Phys.Rev. 112 (1958) 1642.
10. F. Herman and S.Skillman, Atomic structure cal-
culations (Prentice-Hall, Englewood Cliffs, New
Jersey, 1963).

INFORMATION THEORY IN QUANTUM STATISTICAL MECHANICS

P. A. B E N I O F F
Argonne National Laboratory, Argonne, Illinois 60440

Received 5 January 1965

Since the advent of i n f o r m a t i o n t h e o r y s o m e Th e n e c e s s i t y of this r e s t r i c t i o n can be s e e n

a t t e m p t s have been made to r e l a t e it to quantum by c o n s i d e r a t i o n of the e x p r e s s i o n s f o r the p a r -
s t a t i s t i c a l m e c h a n i c s . In p a r t i c u l a r it has b e e n tition function Z(A 1 - . . An) and the m a x i m u m
s u g g e s t e d [1, 2] that the l e a s t b i a s e d p r e d i c t i o n entropy d en si t y o p e r a t o r 0 given by [1, 2].
of p r o p e r t i e s of a s y s t e m s u b j e c t to p r i o r know- n
ledge of the e x p e c t a t i o n v a l u e s of a s e t of o b -
s e r v a b l e s Oi, i = 1, 2 . . . n , is obtained by u s e
Z(A1 ... Xn): Tr lexp (-i~=lXiOi)j (1)

of the m a x i m u m entropy d e n s i t y o p e r a t o r , p. One and

o b t a i n e s p by u s e of L a g r a n g e m u l t i p l i e r s to n
m a x i m i z e the i n f o r m a t i o n g i v e n by I = - T r p In p
s u b j e c t to the n+ 1 c o n s t r a i n i n g conditions (Oi) =
(2)
Trp 0 i i= 1... nandTrp = 1. No m e n t i o n has 0- Z(A~... An)
been made of any r e s t r i c t i o n s on the s e t of ob-
s e r v a b l e s 0 i , so one is left with the i m p r e s s i o n w h e r e the X1 . . . An a r e the L a g r a n g e m u l t i p l i e r s
that such a t r e a t m e n t is v a l id f o r an a r b i t r a r y and the i n i t i al c o n s t r a i n t s c o n s i s t of t h e v a l u e s
set. of (Oi) i = 1 . . . n. If the eigenfunctions of 0 c o n -
The p u r p o s e of this note is to point out that s i s t of the b a s i s s e t la) which is d e n u m e r a b l y
the s e t of o b s e r v a b l e s is not a r b i t r a r y in that at infinite, then eq. (1) g i v e s
l e a s t one o b s e r v a b l e m u s t have the p r o p e r t y t h a t
n
its diagonal m a t r i x e l e m e n t s in the e i g e n f u n c t i o n
r e p r e s e n t a t i o n of p m u s t be monotonic i n c r e a s i n g .
a=O i=I
T h i s was pointed out s o m e t i m e ago f o r the s p e -
c i a l c a s e in which the i n i t i a l c o n s t r a i n t , b e s i d e s Since Xi >i 0 f o r e a c h i, this su m e x i s t s only if
T r p = 1, is the v al u e of ( /~ w h e r e H is t h e
H a m i l t o n i a n [3], but a p p e a r s to have been o v e r -
(~ Loil~)<(~ + 110il~ + 1) (4)
looked in m o r e g e n e r a l a p p l i c a t i o n s . f o r a l l a f o r at l e a s t one o b s e r v a b l e in t h e s e t .

496
Volume 14, number 3 PHYSICS LETTERS 1 February 1965

It is s u f f i c i e n t t h a t t h e i n c r e a s e of (a I Oil ot) w i t h o b s e r v a b l e s in the r e s t of t h e set.

be f a s t e r t h a n l o g a r i t h m i c , i.e. [3] In c o n c l u s i o n , it s h o u l d be noted that condi-
t i o n s (4) and (5) a r e n e c e s s a r y r e s t r i c t i o n s only
(~loil~) in i n f i n i t e d i m e n s i o n a l v e c t o r spaces.
lim In ~ oo (5)

F o r e x a m p l e , if t h e s e t of o b s e r v a b l e s Oi, i =
1 . . . n a r e a l l p r o j e c t i o n o p e r a t o r s [2] P a =
l a ) ( a I w h e r e ~ = 0, 1 . . . n - 1, t h e n c o n d i t i o n (4)
is not s a t i s f i e d and Z(k 1 . . . An) = o~ and p = 0.
H o w e v e r , if one o b s e r v a b l e in t h e s e t s a t i s f i e s
c o n d i t i o n s (4) and (5), as t h e H a m i l t o n i a n d o e s ,
f o r e x a m p l e , t h e n Z and p a r e f i n i t e f o r a r b i t r a r y
References
1. E . T . J a y n e s , Phys.Rev. 106 (1957) 620; 108 (1957)
171.
2. A.Katz, Nuovo Cimento 33 (1964) 1544, 1552.
3. J.Von Neumann, Mathematical foundations of quan-
hnn mechanics, (Princeton University P r e s s , 1955)
p. 390.

QUANTUM CORRECTIONS FOR SECOND VIRIAL COEFFICIENTS

USING DIFFERENT LENNARD-JONES (m-n) POTENTIALS
AND APPLICATION TO HELIUM

R. H A B E R L A N D T
Arbeitsstelle p~r Statistische Physik der Deutschen Akadernie
der Wissenschaften zu Berlin, Leipzig

Received 4 January 1965

U s i n g t h e S l a t e r s u m we get an e x p r e s s i o n f o r t e m p e r a t u r e r a n g e 0.30 ~< T* ~< 400.

the s e c o n d v i r i a l c o e f f i c i e n t and its q u a n t u m c o r - A p p l y i n g eq. (2) to h e l i u m we u s e f i r s t l y e x -
r e c t i o n s [1]. F o r t h e L e n n a r d - J o n e s (m-n) p o t e n - p e r i m e n t a l v a l u e s of W h i t e [2] (45 < T < 300°K :
tial c a s e 1) and s e c o n d l y of W h i t e [2] and Y n t e m a
1 [3] (45 < T<1473OK : c a s e 2) to fit the t h e o r e t i c a l
{(~)n (__~)rn} , 1 n-m
(~),m,_/nn v a l u e s . T h i s is p o s s i b l e up to about 900°K. We
h a v e u s e d the m e t h o d of l e a s t s q u a r e s . F o r
m o r e d e t a i l e d i n f o r m a t i o n a n o t h e r m e t h o d is
the i n t e g r a t i o n o v e r t h e c o o r d i n a t e s p a c e g i v e s : u s e d : W e r e w r i t e eq. (2), so that we get a as a
s(n-m) + u(n-2) + 3
n
B -

s(n-m) - 2u + 3
b(S)(rn, n) -kOv + klus + k2vs 2 + k3us 3 ct n F (ms - 3 + 2u)
V n " (2)
dunn2Usl
k~z u =- 0 (g = 0 , 1, 2, 3) f o r ~ > v; d v = c o n s t . f u n c t i o n of < w i t h the p a r a m e t e r T. T h i s m e t h o d
k g v d e p e n d on rn and n only. t a k e s into a c c o u n t t h a t the q u a n t u m c o r r e c t i o n s
U s i n g b(S)v(6, 8) (0 --< s ~< 51), b(S)v(6, 9) a r e a l s o f u n c t i o n s of ~ and ~, so t h a t it b e c o m e s
(0 ~< s < 60) and b(S)v(6, 12) (0 < s < 40) [1] an i t e r a t i v e m e t h o d . F o r s o m e t e m p e r a t u r e s of
the s e c o n d v i r i a l c o e f f i c i e n t , its d e r i v a t i v e s c a s e 1 one f i n d s a c o m p a r i s o n of the c a l c u l a t e d
w i t h r e s p e c t to t e m p e r a t u r e and the z e r o - p r e s - and t h e e x p e r i m e n t a l v a l u e s in t a b l e 1. F i g u r e 1
sure Joule-Thomson coefficient are calculated s h o w s t h e L e n n a r d - J o n e s (6-9) and (6-12) p o t e n -
w i t h t h e i r f i r s t t h r e e q u a n t u m c o r r e c t i o n s in t h e t i a l s and an exp - s i x p o t e n t i a l (MR 5) [4]. F o r h e l l -

197