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IL NUOVO

I~IVISTA ORGANO
SOTTO E DEL

CIMENTO
ITALIANA
NAZIONALE PER L'ENERGIA

INTE RNAZIO>TALE DI FISICA


RICERCI~E NUCLEAI~E CONSIGLIO DELLE

DELLA
DEL

SOCIETA

GLI AUSPICI COMITATO

NAZIOIgALE

VOL. L I V B , N. 2

Serie decima

11 Aprile 1968

The Pair Potentials of Ne, Ar, Kr and Xe from Solid-State Data.


I. J. ZUCKER Physics Department, University o] Surrey - .London
(ricevuto il 12 Agosto 1967; manoscritto revisionato ricevuto il 24 Ottobre 1967)

-Assuming only two-body interactions, theoretical solidstate isotherms arc calculated for Ne, Ar, Kr and Xe for various pairpotential functions. By comparison of the theoretical and experimental isotherms the < best ~ pair potential is easily determined. The effect of ~ long-range three-body forces on the determination of the pair potential functions of the heavier inert g~scs from solid-state datg~ is also investigated. The inclusion of the 3-body lattice energy alters the parameters of a given pair potential considerably, but does not affect ~he theoretical isotherms obtained. Summary.

1.

Introduction.

Direct q u a n t u m mechanical calculation of the complete pair-potential function, F(R), acting between pairs of rare gas atoms are v e r y difficult to perform. 9(R) is usu:~lly inferred empirically from t h e r m o d y n a l n i c properties. Usually gaseous or solid-state data is used. Some gaseous data such as the second virial coefficient, B2, have the advantage of depending only on ~0(_R). B u t it has been shown (1) to be impossible to d e t e r m i n e a unique ~0(R) from B2 d a t a alone. On the other ]land certain solid-state properties easily differentiate different forms of ~(_g), b u t it is now recognized t h a t 3-body forces play an i m p o r t a n t role in the solid. F u r t h e r , the theoretical evaluation of solid-state properties involves the i n t r o d u c t i o n of ~ model to facilitate calculation. However, we

(1) J. B. KELLER and B. ZUMINO: Journ. Chem. Phys., 30, 1351 (1959).
12 - I1 .uovo Cimento B .

178

L J. ZUCKER

shall use solid-state d a t a since b y e m p l o y i n g certain t h e r m o d y n a m i c properties t h e effect of a given crystal model is nullified. The effects of 3-boyd forces will also be considered. T h e t h e r m o d y n a m i c p r o p e r t i e s which are chosen to d e t e r m i n e ~(i~) are those which at a n y fixed t e m p e r a t u r e are v o l u m e d e p e n d e n t only. These p r o p e r t i e s depend only on t h e inter-particle s e p a r a t i o n in the crystal a n d hence will be sensitive to t h e f o r m of ~(/~). T e m p e r a t u r e d e p e n d e n t p r o p e r t i e s such as specific h e a t will not be considered since t h e i r theoretical evaluation depends v e r y m u c h on t h e m o d e l of t h e crystal employed. This is opposed to t h e view of G V G G v , ~ I ~ a n d McGLAstL~I~ (3) who l a y m o r e stress on using specific h e a t a n d e n t r o p y d a t a to d e t e r m i n e ~(/~). BOATO (3) a n d POLLACK (4) h a v e r e c e n t l y m a d e excellent reviews on t h e e x p e r i m e n t a l a n d theoretical p r o p e r t i e s of t h e inert-gas solids and m a n y references m a y be found there. T h e procedure a d o p t e d h e r e for d e t e r m i n i n g t h e best fitting ~{/~) was as follows. A suitable a n a l y t i c f o r m with a n u m b e r of u n d e t e r m i n e d p a r a m e t e r s was chosen. These p a r a m e t e r s were e v a l u a t e d f r o m e x p e r i m e n t a l p r o p e r t i e s of t h e solid at the absolute zero. Three quantities were available n a m e l y t h e h e a t of sublimation, Ho, a lattice c o n s t a n t - - t h e choice here was t h e nearestn e i g h b o u r distance i~o, a n d t h e i s o t h e r m a l conpressibility, Ko. The values used are shown in T a b l e I. To t e s t the c o m p l e t e l y d e t e r m i n e d p o t e n t i a l s t h u s obtained, theoretical i s o t h e r m s were t h e n e v a l u a t e d at various t e m p e r a t u r e s a n d c o m p a r e d with available e x p e r i m e n t a l data. I n this w a y t h e ~(best )~ fit q~(./~) could be identified. TABL~ I. Gas

//o
(cal/mole) 448 1846 2666 3828

Density (gm/em3) 1.508 1.771 3.094 3.782

R0

KT~o

(angstrhm) 3.1563 3.7549 3.9910 4.3356

cm/dyn 2.101 0.90 0.375 0.32 0.28

~]eon

Argon Krypton Xenon


All data from ref. (').

2. -

Theory.

T h e f r e e energy of a c r y s t a l a t the absolute zero, F0 is a function of 7~o only a n d is equal to Ho. F r o m well-known t h e r m o d y n a m i c relations the eqs. (2.1)-(2.3) (2) E. A. GUOOE~I~EI~ and M. L. McGLAs~A~: Proc. Roy. Soe., A 255, 456 (1960). (a) G. BOATO: Cryogenics, 4, 65 (1964). (4) G. L. POLLACK: Rev. Mod. Phys., 36, 748 (1964).

THE PAIR POTENTIALS

O F NO, At, Kr A N D

Xo

FI~O~[ SOLID-STATE

DATA

179

follow (2.1) (2.2) Yo(-Ro) = - - Ho, 2 = -- \ ~ ] , = -- \~-~1 l ~ ] '

(2.3)

Ko--

g-? ~=

v t \ e V l ~eR~/ + \ ~ l ~ g g V ]

"

For face-centred cubic structures which is the lattice structure of the elements considered here V = 2V/?s/~/2. A n expression for Fo in terms of Ro is required and we write

(2.4)
where

Fo = (P(2L) -j- ( 2 Z ) + ( 3 L ) + (P(3Z),

~b(nZ) = n - b o d y static lattice e n e r g y ,

qS(nZ) =

n - b o d y zero-point e n e r g y .

For the m o m e n t we shall only include 05(2L) and ~5(2Z) and consider higher-body terms in Sect. 5. I t is convenient to introduce the expressions

( 2n

where ~ means s u m m a t i o n over all pairs of lattice points of a given lattice from one lattice point taken as origin. Then it is easily shown t h a t

(2.5)

2g ,P(2L) = ~ P o .

Accurate expressions for (2Z) are known under certain conditions, qS(2Z) m a y be split into two p a r t s - - o n e contribution due to t h e h a r m o n i c vibrations of the lattice points and the other due to anharmonie vibrations. The latter are ~asually t r e a t e d as perturbations. I n this case we have the accurate expressions for qS(2Z-harm) (~) (2.6) ~(2Z-harm) -----1.0227i~N ,

(~) C. Do~s and L. SALTER: Phil..Slag., 43, 1083 (1952).

180

I.J.

ZUCI~ER

a n d qS(2Z-anharm) (~)
(2.7) q~(2Z-anharm) = 6 m

[(1.0227)T

q~lv

-- 5.928

(7)]
,n 2

H o w e v e r , b o t h these expressions consider only nearest neighbours, a n d f u r t h e r the leading-term a p p r o x i m a t i o n is m a d e . This neglects all t e r m s such as 90"-1/R c o m p a r e d with q9~ a n d it has been p o i n t e d out (m) t h a t in t h e case of t h e a n h a r m o n i e zero-point energy the l e a d i n g - t e r m a p p r o x i m a t i o n yields errors of the order of m a g n i t u d e of the effect studied. Also a l t h o u g h one requires expressions for the a n h a r m o n i e free energy at finite t e m p e r a t u r e s in order to calculate the i s o t h e r m s the expressions k n o w n are valid only a t highor l o w - t e m p e r a t u r e limits. F o r these reasons ~ve shall e m p l o y an Einstein single-p~rticle model which suffers none of these d i s a d v a n t a g e s (~'~). I n this m o d e l one particle is t a k e n as typical of all others ~nd is assumed to m o v e a b o u t its equilibrium position in the m e a n field of all the others. I f ~ is its d i s p l a c e m e n t from equilibrium it m a y be shown t h a t the p o t e n t i a l e n e r g y of d i s p l a c e m e n t is given b y
(2.8)

V = P~ ~ + P~ ~4 + / ) 6 ~0 -..,

t h e first t e r m being t h e h a r m o n i c energy the others being a n h a r m o n i c terms. I f this p o t e n t i a l is s u b s t i t u t e d into the SchrSdinger equation the eigenvalues m a y be found numerically e x a c t l y (12). I f t h e a n h a r m o n i c t e r m s are t r e a t e d as p3rturb~tions we h~ve to second-order p e r t u r b a t i o n t h e o r y t h e e n e r g y levels (~2) (2.9)
E ( n , l) = E ( h a r m ) + E(first-order a n h a r m ) + E(seeond-order a n h ~ r m ) ,

(2.~o)
(2.11)

E(harm)=(4n+2l

+ 3)]~ ~ 2 ~

E(first-order a n h a r m ) = (6n 2 + 6nl 4- 9n + l ~ + 4l 4- 3.75)~ ~ -P4 2mP~ '

(6) A. A. MARADUDIN and_ P. A. FLINN: Anon oJ Phys., 22, 223 (1963).

(~) :P. LLOSD: A~st. Journ. Phys., 17, 269 (1964). (s) W. H. K. BARRON and 1K. L. KLEIN: Proc. Phys. Soc., 85, 533 (1965).
(9) (lo) (11) (12) j. H. ttEKEL: Journ. Chem. Phys., 23, 681 (1955). R. P. Hu~sT and J. M. H. LEVETT: Journ. Chem. Phys., 34, 54 (1961). I. H. HILLI]~R and J. W~tr.KLEY: Jour~. Chem. Phys., 41, 2168 (1964). I. J. ZtrCKER: Proc. Camb. Phil. Soe., 60, 273 (1964).

TYcIE FAIR POTENTIALS OF 7-~e, A r ,

K r AND X o FROM SOLID-STATE DATA

] 8[

(2.12) E(second-order anharm) = (20n 3 + 45n 2 ~- 40n + 30n ~l +


+ 1 2 n l 2 ~ 4 2 n l + 1s + 7.5l 2 + 17.75l + 13.125)h a
--

P~
(2mP~) -~

(7.5n 3 4- 17n ~ + 14.8125n + l l n ~ l + 4.75nl 2 @ 16.5nl +

p~

+ 0.5/a + 3.25/2 -]- 6 . 8 7 5 / + 4.6875) (2m.P~'~ P2 ' n is the radial q u a n t u m n u m b e r a n d 1 is t h e orbital a n g u l a r - m o m e n t u m q u a n t u m number. E a c h can t a k e all positive integral values i n d e p e n d e n t l y of one another and t h e r e is ~ (2/+1)-fold d e g e n e r a c y associated with e a c h / - v a l u e . The zero-point e n e r g y per particle is o b t a i n e d b y setting n and 1 equal to zero. Thus the E i n s t e i n model yields for the harmonic zero-point energy 3 ] i x / ~ / 2 m . This can be c o m p a r e d with the exact result b y neglecting ~'//~ c o m p a r e d with ~" in P2 a n d taking the s u m in P~ over the twelve n e a r e s t neighbours only. Thus P2 becomes 12~o'/6 and t h e Einstein h a r m o n i c zero-point energy yields 1.061 ~ ( 8 ~ " / m ) which differs b y only 3 % f r o m t h e exact result. No similar comparison can be m a d e b e t w e e n the exact a n h a r m o n i c t e r m and t h e Einstein first-order a n h a r m o n i c t e r m . B u t it is known (13) t h a t even the exact ~nharmonic t e r m s h a v e negligible effect on the p o t e n t i a l p a r a m e t e r s of xenon and k r y p t o n , a l m o s t negligible effects in argon, and even in t h e case of neon the effects are only of the order of (3 -- 4) % . H e n c e though t h e Einstein results only give t h e order of m a g n i t u d e of a h n a r m o n i c effects it is a d e q u a t e to use t h e m . F u r t h e r in using the Einstein model we derive t h e benefit of being able to calculate t h e n e x t - o r d e r a n h a r m o n i c t e r m and thus check if p e r t u r b a t i o n t h e o r y is valid. I t is also not necessary to m a k e the l e a d i n g - t e r m a p p r o x i m a tion and all neighbour interactions m a y be t a k e n into account. Finally t h e p a r t i t i o n function, Z, of the crystal is easily r e p r e s e n t e d b y

and hence all t h e t h e r m o d y n a m i c p r o p e r t i e s of the crystal at all t e m p e r a t u r e s are easily evaluated. The a d e q u a c y of p e r t u r b a t i o n t h e o r y has been checked b y considering typical potentials of neon and argon previously d e t e r m i n e d f r o m gaseous data. I t is these two elements which h a v e the largest p e r c e n t a g e of a n h a r m o n i c energy. I t was found for neon at T = 0 t h a t qS(2L) ~ - - 600 cal, ( 2 Z - h a r m ) ~ 130 cal, (2Z-first a n h a r m ) 13 cal, ( 2 Z - s e c o n d a n h a r m ) ~ 1 cal. F o r argon it was found qS(2L) ~ - - 2000 cal, ~b(2Z-harm) ~ 150 cal, (2Z-first a n h a r m ) ~ 4.1 cal while ~b(2Z-seeond a n h a r m ) ~ 0.03 cal. These figures show conclusively t h a t

(za)

j.

S.

BRowsr:

Proc. Phys. Soc., 89, 987 (1966).

182

i..1. ZUCKER

p e r t u r b a t i o n t h e o r y is a d e q u a t e at T = 0. A t elevated t e m p e r a t u r e s m o r e care is required. I t should be pointed out t h a t the energy levels given b y (2.10)-(2.12) are in f a c t a n a s y m p t o t i c series. F o r large n (or l) t h e p e r t u r b a tion t e r m s become as large as the u n p e r t u r b e d t e r m s since the l a t t e r depend only on n while the p e r t u r b a t i o n t e r m s d e p e n d on n 2 and n 3. The error in an a s y m p t o t i c series is of t h e order of the first t e r m neglected. This has the f o r m

O(nd) h 4 (2mP~)~, a n d even at the melting points of the elements considered here this has b e e n shown to give a negligible contribution to the p a r t i t i o n function. H e n c e alt h o u g h second-order p e r t u r b a t i o n t h e o r y is necessary at elevated t e m p e r a t u r e s it is also sufficient.

P8

3. - The pair potential. I n spite of recent opposition to simple r e p r e s e n t a t i o n s of potentials engend e r e d b y the work of GUGGENKEI~ and )ICGLASItAN (2) we shall continue to use t h e forms of ~(R) suggested b y KmARA (14) a n d LENNAI~D-JONES. I t is e v i d e n t f r o m the w o r k of GUGGENB:EI~ a n d IV[CGLAsI-IANt h a t t h e i r six-param e t e r p o t e n t i a l is useful only in r e p r e s e n t i n g t h e situation close to t h e minim u m of ~0(R). W i t h situations in which the molecular separation is different to t h e m i n i m u m , e.g. in a crystal u n d e r pressure, t h e i r p o t e n t i a l breaks down. Thus it is unable to give a reasonable crystal i s o t h e r m even for only m o d e r a t e pressures. Simple potentials on the other h a n d can represent high-pressure d a t a successfully as will be seen, and t h e i r p e r f o r m a n c e at low pressures is not v a s t l y inferior to t h e m a n y - p ~ r a m e t e r potentials. T h e t w o - b o d y p o t e n t i a l s investigated h e r e are of a f o r m suggested b y KII~AlCA (14), n a m e l y (3.1)

[in* - r!
where (_M'~ ~":-e~
C(M)-: \ 6-!

~ R * - ~! ] '
R*=
'

6
"M--6

R
(~

R~ln ----"(1 -- y) - a, s a n d /m~. h a v e t h e usual meanings. (14) T. KII-IARA: R e v . . ] [ o d . P h y s . , 25, 831 (1953).

+ ~' ,

THE PAIR POTENTIALS

O F No, At, K r A N D

No

FROM

SOLID-STATE

DATA

183

I f M is c h o s e n (3.1) r e p r e s e n t s ~ t h r e e - p a r a m e t e r p o t e n t i a l w i t h e, a a n d y - - c a l l e d t h e c o r e - - a s u n k n o w n p a r a m e t e r s . I f y = 0, (3.1) r e d u c e s to t h e w e l l k n o w n L e n n a r d - J o n e s (L-J) p o t e n t i a l . T h i s is o n l y a t w o - p a r a m e t e r p o t e n t i a l a n d o n l y eqs. (2.1) a n d (2.2) n e e d b e u s e d t o find e a n d (~. I n t h i s case Ko m a y be e v a l u a t e d f r o m (2.3) a n d c o m p a r e d w i t h e x p e r i m e n t as a c h e c k . T h e p a r a m e t e r s of b o t h L-ff a n d K i h a r a p o t e n t i a l s w e r e e v a l u a t e d for n e o n , a r g o n , k r y p t o n a n d x e n o n for s e v e r a l v a l u e s of M : T a b l e s I I - V . I s o t h e r m s w e r e e v a l u a t e d for e a c h p o t e n t i a l a t t h o s e t e m p e r a t u r e s f o r w h i c h e x p e r i m e n t a l TABLE I I a). - .Neon L - J parameters. ~ is given in angstrSm. A* is the quantum parameter h/(~ ~ / ~ ) .
M e/k a A*

Cale. KT-o 1.18 1.00 0.88

10 12 14

33.4 36.5 38.7

2.774 2.776 2.783

0.608 0.581 0.562

TABLE I I b ) . - Veon Kihara parameters, a is given in angstrSm. A* is the quantum p a r a m e t e r h/(a ~m-~). A* 10 12 14 39.6 39.0 38.1 2.777 2.779 2.782 0.558 0.562 0.567 0.154 0.065 --0.016

TABLE I I I a ) . - Argon L - J parameters, a is given in angstrSm. A* is the quantum )arameter h/( a v'~'~). M 10 12 14 ~/k 111.0 119.4 125.1 a 3.397 3.400 3.410 A* 0.194 0.186 0.182 Cale. K~.o 0.452 0.381 0.330

TABLE I I I b). - Argon Kihara parameters, a is given in angstrSm. A* is the quantum p a r a m e t e r h/(a v/m-~). M 10 12
14

~tk

o-

A*

122.7 120.4 117,2

3.396 3.400 3.406

0.184 0.186 0.188

0.105 0.009 - - 0.079

184

i. ~.

ZUCKE~

TABL~ I V a). - Krypton L - J parameters, a is g i v e n i n a n g s t r 6 m . ) a r a m e t e r h/( a V-m"~). M

A* is t h e q u a n t u m

,/k

(Y

A*

CaIc. K ~ . o

10 12 14

153.6 164.7 171.9

3.631 3.635 3.646

0.106 0.103 0.100

0.371 0.311 0.268

TABLE I V b). - Krypton K i h a r a parameters, a is g i v e n i n a n g s t r S m . A* is t h e q u a n t u m p a r a m e t e r h/(a ~ / ~ ) . M */k a A* y

10 12 14

165.7 162.3 157.7

3.630 3.635 3.642

0.102 0.103 0.105

0.081 --0.012 --0.109

TABLE V a). - Xenon L - J parameters, a is g i v e n i n a n g s t r S m . p a r a m e t e r h/(a ~/m-~e). M A*

A* is t h e q u a n t u m

Calc. K r _ o

10 11 12 14

216.2 224.8 231.5 241.3

3.955 3.956 3.960 3.972

0.066 0.064 0.063 0.062

0.329 0.300 0.275 0.237

TABLE V b). - Xenon K i h a r a parameters, a is g i v e n i n a n g s t r S m . A* is t h e q u a n t u m p a r a m e t e r h/(a v/m-~). M


elk o"

A*

10 12 14

235.1 230.3 223.9

3.955 3.960 3.967

0.063 0.064 0.064

0.092 --0.006 - - 0.097

THE PAIR

POT]~NTIALS

OF

Ne, A t , K r

AND

NO

FROM

SOLID-STATE

DATA

185

d~ta were available. krypton (77 ) ( ~ ) a n d

T h e d a t a a v a i l a b l e w e r e f o r n e o n (4), a r g o n (65 a n d 77), x e n o n (:6) f o r a r a n g e isotherms have of t e m p e r a t u r e s . Some typical b e e n i l h ~ s t r a t e d i n F i g . 1-6.

t h e o r e t i c a . 1 a,n d e x p e r i m e n t a l

24' E

22
20

\
i

~x

18
8
i i i i i ~ i i r i

)_

i "--~-i

4-

8
pressure

12 (kb)

16

20

8
pressure

12 , kb:

16

20

Fig. 1. - T h e o r e t i c a l i s o t h e r m s of solid n e o n a t 4 K. o E x p e r i m e n t a l p o i n t s , STEWART (1956). L - J M = 10; - L - J M = 12; KIHA~A; L - J M = 14.

Fig. 2. - T h e o r e t i c a l i s o t h e r m s of solid a r g o n a t 65 K. o E x p e r i m e n t a l p o i n t s , STEWART (1956). - - - - - L - J M = 10; - L - J M = 12 a n d KIgARA; -- -- -- L - J M = 14.

24

"~22 20
18

x"" "~ " ' - . ~ ~


~

~
, 1~2 , p

-~--~
16, ~
L-~ 20o

, 4

250

2
pressure kb::

pressure

(kb)

Fig. 3. - T h e o r e t i c a l i s o t h e r m s of solid a r g o n a t 77 K. o E x p e r i m e n t a l p o i n t s , ST~WA_~T (1956). - - - - - L - J M---- 10; L - J M = 12; . . . . . KIHARA; -----L-J M = 14.

Fig, 4. - T h e o r e t i c a l i s o t h e r m s of solid k y p t o n a t 77 K. o E x p e r i m e n t a l p o i n t s , STEWART (1955). - - - - - - L - J M=10; - L - J M = 12; . . . . . KIHARA;


-----L-J M=14.

(15) j . W . STEWART: Phys..Rev., 97, 578 (1955); Journ. Chem..Phys. Solids, 1, 146 (1956). (:G) j . R. :PACKARD a n d C. A. SWANSON: Journ. Phys. Chem. Solids, 24, 1405 (1963).

186

L J. ZUOKER

36 34 E 32
(D

32

%'!'i--....
4 8 12 16 20
pt'essure (kb)

8
pressuce (kb)

16

20

280

:Fig. 5. - ThcoreticM isotherms of solid xenon at 0 K. o Experimental points, PACKARD and SWANSON (1963). - - - - - - L - J M = 10; - L - J M = 12;
KIHARA; L-J M= '4;

....

L - J M - - 11.

Pig. 6. - Theoretical isotherms of solid xenon at 100 K. o Experiment a l points, PACKARD and SWE~SO~ (1963). ------ L-J M=10; - L-J M=12; ---L-J M=14; .... L-J M=ll.

4.

Discussion.

S e v e r a l g e n e r a l f e a t u r e s s h o w e d on p l o t t i n g t h e t h e o r e t i c a l i s o t h e r m s . All the Kihara potentiMs gave isotherms which could not be distinguished from one another. On the other hand the L-J potentials with different M clearly gave differentiable isotherms especially at high pressures. The best fitting p o t e n t i a l s w e r e e a s y t o p i c k out. F o r n e o n t h e b e s t fit p o t e n t i a l w a s t h e L - J w i t h M = 12. F o r a r g o n t h e K i h a r a or L - J w i t h M = 12 g a v e e x c e l l e n t a g r e e m e n t a t T = 65 a n d g o o d a g r e e m e n t a t T = 77 . F o r x e n o n b o t h a t Y = 0 a n d T = 100 t h e L - J p o t e n t i a l w i t h M - - - - 1 1 was t h e b e s t . N o clearc u t b e s t fit p o t e n t i a l c o u l d b e d e t e r m i n e d for k r y p t o n , b u t i n t h i s c a s e t h e e x p e r i m e n t a l i s o t h e r m h a s o n l y b e e n d e t e r m i n e d t o 4000 a t m o s p h e r e s . T h i s i l l u s t r a t e s t h e n e c e s s i t y for h a v i n g g o o d h i g h - p r e s s u r e d a t a a v a i l a b l e a s i t is ~lear from the other cases how these data can decide the best fitting theoretical potential. I t is v e r y s a t i s f a c t o r y w h e n t h e s a m e p o t e n t i a l g i v e s g o o d a g r e e m e n t for i s o t h e r m s a t w i d e l y d i f f e r e n t t e m p e r a t u r e s as w a s t h e case w i t h t h e L - J M ~ 11 f o r t h e case of x e n o n a n d t o a l e s s e r e x t e n t t h e L - J M = 12 p o t e n t i a l for a r g o n . I t s h o u l d b e p o i n t e d o u t t h a t t h e o n l y p o i n t a t w h i c h t h e o r y a n d exp e r i m e n t m u s t n e c e s s a r i l y a g r e e is for w h e n b o t h t h e p r e s s u r e a n d t e m p e r a t u r e a r e z e r o as t h i s is t h e o n l y p o i n t u s e d for f i x i n g t h e p o t e n t i a l p a r a m e t e r s . H e n c e , a g r e e m e n t of a t h e o r e t i c a l a n d e x p e r i m e n t a l i s o t h e r m a t t e m p e r a t u r e s well

THE P A I R P O T E N T I A L S OF ~ e ,

Ar, Kr

AND X o

FROM S O L I D - S T A T E DATA

187

above zero strongly suggested t h a t the potential used was the ((best ~) representation of the pair interaction. However, one must be careful not to claim t h a t this is the only possible representation in view of the neglect of higherbody forces.

5. - The effect of long-range 3-body interactions on the determination of the pair potential.

The first calculation of 3-body forces was made b y AXILROD and TELLER (17) who applied third-order p e r t u r b a t i o n t h e o r y to the interaction of a triplet of atoms. I n addition to the three pairwise van der Waals interaclions t h e y also obtai~led a nonvanishing expression for the triplet interactions of the three particles. This was (5.1) V(3) _ v(cos 0~ cos 02 cos 03 + 1)
--p3 23 31 ~-v12 Ra R3

02, 03 are the interior angles of the triangle formed b y the particles with sides R12, R23 and R21. L a t e r AXILROD (~) showed v = (9/16)I~ 2 where I is the ionization e n e r g y and ~ the polarizability of the atom. Recently BELL and KINGSTON (a9) have evaluated v from first principles with a reported accuracy of 10 % and within this limit their v~lues agree with Axilrod~s. They disagree with the values of v calculated b y KIHARA (20) and used b y R o s s I and DAN0~ (21). The values of BELL and KInGSTOn" are used here. AXILROD also culculated the total energy of interaction of triplets of atoms in a facecentred cubic lattice and showed this to be

01,

(5.2)

~(3L) =

56.7 ~ .

Since v is positive this appears as a repulsive t e r m in the lattice energy. Values for ~5(3L) at T = 0 have b~en given in Table V I and it m a y be seen t h a t t h e y are far from negligible. This merely represents the long-range p a r t of the t h r e e - b o d y potential. JANSEN (22) has evaluated the short-range exchange 3 - b o d y forces and although

(17) B. (is) B. (~s) R. (20) T. (21) j. (2:) L.

M. AXILROD and E. TELLER: Journ. Chem. Phys., l i , 299 (1943). M. AXILROD: Journ. Chem. Phys., 19, 724 (1951). J. :BELL and A. E. KINGSTON: Proe. Phys. Soe., 88, 901 (1966). KIHARA: Adv. Chem. Phys., l, 267 (1958). C. RossI and F. DANON: Journ. Phys. Chem. Solids, 26, 1093 (1965). JANSEN: Phys. Rev., 135, A 1292 (1964).

188

I.

ft. Z U C K E R

TABLE VI. Gas


~6on

H o (eal/mole) 448 1846 2666 3828

(erg (A)9.1012) 1.677 74.48 223.7 749

~b(3L) (cal/mole) 14.68 136.6 236.9 376.6

Argon Krypton Xenon

he gives no explicit expression, he has shown t h e y h a v e the s a m e sign a n d a n g u l a r dependence as (5.1). However, SW:E~T]BERG(23) has cast some d o u b t on t h e validity of J a n s e n ' s assumptions a n d owing to the general u n c e r t a i n t y concerning short-range 3-body forces t h e y are neglected here. The zero-point e n e r g y due to 3-body interactions can be e v a l u a t e d simply on a n Einstein m o d e l (~4,~5) b u t it is e x p e c t e d t h a t this effect will be small and is also neglected here. Thus we will s i m p l y consider t h e effect of t h e long-range p a r t of t h e 3-body interaction on t h e evaluation of t h e p a i r potential. T h e procedure for d e t e r m i n i n g the p a i r p o t e n t i a l is precisely the sume as in Sect. 2 except t h a t in addition to (2L) and qS(2Z) we include ~b(3L) as given b y (5.2) here in t h e equation for F0. As all the properties used a n d calculated are isotropic t h e effect of including ~5(3L) is just to add a k n o w n twob o d y repulsive term. H e n c e in precisely the s a m e w a y as before the param e t e r s of L - J and K i h a r a potentials were e v a l u a t e d including ~b(3L)~ and t h e n isotherms calculated also with ~b(3Z). The p a r a m e t e r s of the p r e v i o u s l y found best fit potentials found with and w i t h o u t the t h r e e - b o d y t e r m included are given in Table V I I .
TABLE VII.

Without Gas M

~(3L)

With ~b(3L)

Neon Argon Krypton Xenon

12 12 12 11

36.5 119.4 164.7 224.8

2.776 3.400 3.635 3.956

37.5 128.3 179.8 248.0

2.765 3.368 3.595 3.902

(23) C. E. SWENBERG: Phys. Lett., 24A, 163 (1967). (24) V~. GOTZE and H. SCH,~IDT: Zeits. f. Phys., 192, 409 (1966). (25) G. G. CHELL and I. J. ZVCKE~: Journ. Phys. C (Proc. Phys, Soc.) Ser. 2, l, 35 (1968),

THE PAIR POTENTIALS OF 7-~e, Ar, Kr AND X e FROM SOLID-STATE DATA

189

6. -

Discussion

of r e s u l t s .

Isotherms c~lculated with the t h r e e - b o d y t e r m included are not shown here. This is because although the inclusion of ~5(3L) altered the potential parameters considerably, no detectable effect was found on the isotherms previously calculated. The (~best fit ~ potentials were thus unaltered. As y e t > no explanation of this can be given. The effect of q~(3L) on the potential parameters invariably had the effect of increasing e and of decreasing a for every potential. B o t h are in the direction suggested b y the l~test gaseous data (26). I t is interesting t h a t the gaseous values several years ago (27) for s and a and solid state values calculated without 3-body term~ agreed quite well. As ]ow-t~mperature B2 data became uvai]able the gaseous values of s and a have been altered substantially and now disagree completely with those calculated from solid-state d~ta w i t h o u t 3-body terms. However, the inclusion of 3-body terms in the solid state push the values of s and a in the direction of tile lntest gaseous data. This is illustrated in Table V I I I TABLE VIII. - Argon L-J M = 12.
Gaseous values

Solid-state values

s/k Old (*)


:New (**)

a 3.41 3.28 No ~(3L) ~(3L) included

s/k
119.4 ]28.3 3.400 3.368

119.0 146.8

(*) Ref. (,e). (*') Ref. (,7).

for argon for the L - J M ~ 12 potential. I f JANSEN is right and the shortrange 3-body forces behave in exactly the same way as (5.1) t h e n if t h e y could be included even closer agreement between gaseous and solid-state values might be obtained. I t is still possible to obtain a g r e e m e n t with solid-state isotherms using simple two-p~r~meter potentials of the L - J form. The inclusion of 3-body forces of the long-range t y p e appears to affect only the potential p a r a m e t e r s and not the isotherms. As a possible m e t h o d of studying 3-body forces this approach can only be used qua, litatively, since as previously mentioned all the calculations used

(26} j. I-[. DYI~IOND, M. RIGBYand E. B. SMITIt: Journ. Chem. Phys., 42, 2801 (1965). (27) j. O. HIRSCHFELDER,C. F. CURTISS and R. B. BIRD: ~]lolecular Theory o] Gases and Liquids (New York, 1954).

190

L ~. ZUCK~R

h e r e d e a l o n l y w i t h i s o t r o p i c effects i n the solid. T h e 3 - b o d y t e r m t h e n app e a r s j u s t as a s i m p l e a d d i t i v e k n o w n c o r r e c t i o n to t h e p a i r p o t e n t i a l . T h e s t u d y of a n i s o t r o p i c c r y s t a l p r o p e r t i e s such as t h e elastic c o n s t a n t s C,2 a n d Ca4 w o u l d be m o r e i n f o r m a t i v e . F o r a n f.e.e, c r y s t a l a n d t w o - b o d y c e n t r a l add i t i v e forces C12 is e q u a l to C44 i n classical t h e o r y . SALTER (2s) s h o w e d t h a t even at T = 0 zero-point energy destroyed this equality, b u t the difference c a n b e c a l c u l a t e d i n t e r m s of t h e t w o - b o d y p o t e n t i a l ; 3 - b o d y forces s h o u l d affect t h i s e q u a l i t y m o r e c r i t i c a l l y (~) a n d i n v e s l i g a t i o n of t h i s i~ n o w i n p r o g r e s s (29).

T h a n k s a r e d u e t o B. UTTL'~e { I m p e r i a l College, L o n d o n ) a n d J . WALKLE and K . Iqe ( S i m o n F r a z e r U n i v e r s i t y , V a n c o u v e r ) for h e l p f u l d i s c u s s i o n s .

(28) L. SALTER: Phil. Mag., 45, 360 (1954). (29) G. G. CHELL: Journ. Phys. C (Pvoc. Phys. Soc.), Ser. 2, 1, 266 (1968).

RIASSUNTO

(*)

I n base alle sole interazioni di due eorpi, si ealeolano le isoterme dello stato solido per il Ne, i'Ar, il Kr e lo Xe per varie funzioni del petenziale di eoppia. Confrontando le isoterme teoriche con quelle sperimentali si determina facilmen~e fl (~migliore ~)potenziale di eoppia. Si studia anche l'effetto delle forze di lungo raggio di tre eorpi sulla determinazione delle funzioni del potenziale di coppia dei gas inerti pi~t pesanti in base ai dati dello stato solido. L ' i n c h s i o n e dell'energia di retieolo di 3 corpi altera considerevolmente i parametri di un dato potenziale di eoppia, ma non influisce sulle isoterme teoriehe ottenute.
( ' ) T r a d u z i o n e a cura d d ~ a R e d a z i o n e .

I-lapm,m n o T e m ~ a ~

Ne, Ar, Kr H X e Ha ~ a m ~ l x no T~ep~oMy COCTOS~IO.

PeamMe (*). - - E~nHcTBemro Hpe~xnonaran ~ayx-qaCTn~mm BaanMo~%e~cTann,Bb~nnc~JnoTc~t TeOpeTHqecK~tetl30TepM/~I TBep~ioro COCTO~ffI~q~%J]~Ne, At, Kr H Xe ~U]npa3smnnbix naprmLX n o T e m m a n ~ i x qbyHr~iL l~yTeM cpaB~ermn TeopeTn~ecrnx n a~cnepaMenTa.qbH]alX n3oTepM, J]erKo onpe~enneTcn <<n a n a y q ~ n ~ >> n a p n ~ noTenLman. T a r ~ e nccne)xyeTcn Bym~m]4e3%Yrm~o-~%e~cTByionlnx Tp~xqacTH~],IX CnYtHa onpe~e~erme n a p n ~ x noTeHIlnazq],n3~ix qbyHXLmft~ T~e~brx nnepT~rx ra30B 1~3 )%a_qBJ, no TBep~ioMy cocIX TO~t~mro. Bx~roqenne 9HepFHH Tpex-qacTI4KBO~ pemeTr,H 3Ha~4TeJn,rro yl3Men~eT napaMeTp/,I )IaHrtoro napHoro rloTeHn~a~a, ito Be BY/tt~/eT Ha no~y~ennsle TeopeTitqecKne n3oTepMhI.

(*) llepese3e~to peOamlue~t.

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