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in England and Wales Registered Number: 1072954 Registered office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH, UK

**Molecular Physics: An International Journal at the Interface Between Chemistry and Physics
**

Publication details, including instructions for authors and subscription information: http://www.tandfonline.com/loi/tmph20

**Equation of state of a hard-core fluid with a Yukawa tail
**

Douglas Henderson , Eduardo Waisman Lesser Blum

a b e a b f

, Joel L. Lebowitz

c g d

&

IBM Research Laboratory, San Jose, California, 95193, U.S.A.

**Department of Chemistry, University of Illinois, Urbana, Illinois, 61801, U.S.A.
**

c

**Service de Physique Théorique, Centre d'Études Nucléaires de Saclay, 91190, Gif-sur-Yvette, France
**

d

**Department of Mathematics, Rutgers University, New Brunswick, N.J., 08903, U.S.A.
**

e

**Department of Physics, University of Puerto Rico, Rico Piedras, Puerto Rico, 00931
**

f

**System Science and Software Inc., PO Box 1620, La Jolla, California, 92038
**

g

Belfer Graduate School of Science, Yeshiva University, New York, N.Y., 10033, U.S.A. Available online: 22 Aug 2006

To cite this article: Douglas Henderson, Eduardo Waisman, Joel L. Lebowitz & Lesser Blum (1978): Equation of state of a hard-core fluid with a Yukawa tail, Molecular Physics: An International Journal at the Interface Between Chemistry and Physics, 35:1, 241-255 To link to this article: http://dx.doi.org/10.1080/00268977800100181

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demand. claims. or costs or damages whatsoever or howsoever caused arising directly or indirectly in connection with or arising out of the use of this material. proceedings.publisher shall not be liable for any loss. actions. Downloaded by [Joh Gutenberg Universitaet] at 05:46 12 April 2012 .

. 35. INTRODUCTION The Ornstein-Zernike (OZ) equation for a simple fluid has the f o r m hl~ = c12+ P S h13Ca~dr3. After September. Urbana. and three related approximation schemes. While perturbation theory works rather well for this system. U. . 08903.S.A. the exponential and linearized exponential modifications of the MSA and the generalized MSA all give good results for this system. Rutgers University. b y g(r)=h(r)+ 1. EDUARDO WAISMANt~ D e p a r t m e n t of Chemistry. However. Permanent address: System Science and Software Inc. 1. 241-255 E q u a t i o n o f s t a t e o f a h a r d . and r i j = Ir i . France and L E S S E R B L U M ~ D e p a r t m e n t of Physics. PRF 8429 AC6 and AFOSR Grant No. 10033. t Supported in part by a grant from the Petroleum Research Foundation No. These results are compared with those obtained from perturbation theory. PO Box 1620. N.S. of finding two molecules separated b y a distance r]. LEBOWITZtw Downloaded by [Joh Gutenberg Universitaet] at 05:46 12 April 2012 Service de Physique Th6orique. g(r) [the probability density. Rico Piedras. California 92038. etc. La Jolla. U. Centre d'l~tudes Nucl6aires de Saclay.A. 1977 : Department of Mathematics. the mean spherical approximation (MSA).r j l is the scalar distance between the centres of mass of molecules i and j at position r~ and rj.c o r e f l u i d w i t h a Y u k a w a tail by D O U G L A S HENDERSON I B M Research L a b o r a t o r y . 1. Yeshiva University.Y. wPermanent address: Belfer Graduate School of Science. the MSA is considerably less satisfactory. California 95193. M.A. U.. N. 1Q .1978. JOEL L.MOLECULAR PHYSICS. VOL. Puerto Rico 00931 (Received 17 ffune 1977) We present Monte Carlo results for the equation of state of a fluid in which the intermolecular potential consists of a hard core of diameter a and an attractive tail which is of the form of a Yukawa function. 73-2430B at Yeshiva University.~ exp {-A(r-a)}/r with A= l'8/a. N o . 91190 Gif-sur-Yvette. T h e functions h(r) and c(r) are the total and direct correlation functions. University of Illinois. U.A.S. New Brunswick.1 inside the h a r d core. New York.. T h e total correlation function is related to the radial distribution function ( R D F ) .S. (1) where hlz=h(rl~). San Jose. normalized to unity at large separations.J. For a fluid with a hard core h(r)-. University of Puerto Rico. Illinois 61801.P.

Secondly. i. r>o. its usefulness arises from the fact that in many cases one can obtain a good approximation to g(r) by making a simple ansatz for c(r) and solving (1). r<cr. k is Boltzmann's constant. Hoye and Stell [8] have simplified Waisman's solution. (5) where the identifications K=/3e and z = A are made. for some range of values of A.j For such a fluid. Their analysis is particularly useful in the GMSA. consider a fluid with a pairwise additive potential energy for which the intermolecular potential is Downloaded by [Joh Gutenberg Universitaet] at 05:46 12 April 2012 u(r) = (3) {w(r). This type of procedure. [4] in their work on electrolytes. Waisman's solution. [7] have given series expansions in powers of K and p for the solution.1. was formalized by Hoye et al. [6] to describe accurately hard spheres near a hard wall. r< 1 (2) r > ~. Although there is no real fluid with this intermolecular potential. Because of these applications. If y =g(e+) and a =/3(OP/OP)T (where p is the pressure and p = N / g is the density) are known. Thus. the mean spherical approximation (MSA) of Lebowitz and Percus [3] consists in assuming c(r) = -/3w(r). It has recently been used by Henderson and Blum [5] to give a good description of the properties of hard spheres and by Waisman et al. In addition. has been the object of considerable investigation. Henderson et al. c(r) = K exp [ . Waisman [2] has obtained an analytic solution of equation (1) for the case where c(r) has a ' Yukawa tail '. a qualitative model of a real fluid. This solution is of interest in two contexts. and thus c(r) and h(r).1. Waisman's solution can be regarded as the solution of the MSA for a fluid for which w(r) = . equation (2) can be regarded as the assumed functional form of c(r) for a fluid with some specified intermolecular potential. Waisman et al.A(r.or)] rio . Henderson et al. r>~ (4) (where/3 = 1/kT.e. directly without iteration. [9].z ( r . . which can also be defined graphically [1].242 D. They referred to this as the generalized mean spherical approximation (GMSA). The parameters K and z are then not given a priori in terms of the intermolecular potential b u t are determined by some semi-empirical method. and T is the temperature) together with the exact condition h ( r ) = . J where cr is the diameter of the hard core of the molecules. which is given in terms of a complex set of simultaneous non-linear equations. r> . h(r) = . such a fluid could be. first used by Waisman [1] for hard spheres. First. the Hoye-Stell procedure can be used to compute K and z.o)]/r.~ exp [ . While equation (1) is really nothing more than a definition of c(r). Hoye and Stell [10] and Hoye and Blum [11] have generalized Waisman's solution to the case where c(r) is given by a linear combination of Yukawa functions.

943 2"561 2"921 2"966 3"205 3"971 4"109 4"257 4"490 4"622 Pert 1-811 2-156 2. It should thus be useful in evaluating the strengths and weakness of the M S A and G M S A in treatments of other fluids.00 1.8/a). the intermolecular potential is given by (3) and (5). EXP and GMSA 1.596 2'561 2"806 2"900 3. Table 1.376 2. respectively. in turn. Elk ~ 120 K cr ~ 3"4 A). this system permits a direct comparison of the M S A for a simple fluid with other approximations and with exact (Monte Carlo) results.e.104 3"971 4. 13]. All calculations reported here use this value of A. i.634 2-561 2"821 2"916 3-127 3"971 4"160 4"227 4"365 4"556 0"6 0"8 . T h e s e are the ' e x p e r i m e n t a l ' results.129 3-971 4"143 4"204 4"331 4"509 1Q2 p* 0. MONTECARLOC L U A I N A C L TO S The method employed is identical to that used by Henderson et al.4 T* oo 2. T h i s paper is a necessary step in our study of the interracial regions of this fluid.292 2. In the following sections we then report results obtained from perturbation theory. In the next section we report results of some M o n t e Carlo computations.Equation of state 243 Downloaded by [Joh Gutenberg Universitaet] at 05:46 12 April 2012 In this paper we study the t h e r m o d y n a m i c properties and radial distribution function of a fluid with a hard core plus a Yukawa tail. Values of g(a+) for the Yukawa fluid (~= 1. T h e uncertainty in p V / N k T and U~/N~ is approximately 0.202 2. the M S A and G M S A . essentially the method used by Barker and Henderson [15-17] in their study of hard spheres. 12.561 2"834 2"912 3"140 3"971 4"165 4"235 4"384 4"600 Equation (21) 1.963 2.561 2-815 2"912 3. 2.in table l we do give our values for g(~+).581 3-629 3"646 3"681 3"729 LEXP 1.811 2. The resulting values of g(r) are not given here because of space limitations.05 and 0-005. T h e properties of this model Yukawa fluid are determined by several different methods.717 2.176 2. T h e M C values of p V / N k T and U~/N~ are given in tables 2 and 3.825 2.811 2. the pressure and the internal energy were calculated by averaging over the chain of configurations. The radial distribution function.50 1"00 co 2.811 2. In addition.00 1"50 1"00 ~ 2"00 1"50 1"00 0"70 MC 1. the Yukawa fluid is qualitatively similar to argon for the densities and temperatures of the liquid in equilibrium with its vapour and with about the same potential parameters as the L e n n a r d Jones potential (i.330 2.141 4"203 4-334 4-517 MSA 1. However.768 1.040 2"222 2"460 2"561 2"598 2"681 3.305 2. We have f o u n d that with ~ = l'8/cr.166 2.e.128 2"378 2. Our interest in this Yukawa fluid is due to the fact that expressions for the density profile of this fluid in the simple external potential corresponding to an idealized wall can be obtained [6. [14] in their study of the square-well fluid which was.811 2.

699 GMSA -2"495 -2"595 . pV/NkT MSA Et for t h e Yukawa fluid ( A .655 -5.975 -4.3.573 .017 -4.573 .607 -5.244 T a b l e 2.035 -4.658 -2"495 -2"552 . T a b l e 3.5.3.476 2"301 -0'049 -3"072 4"283 1"992 1"235 -0"288 7-750 4"464 3"373 1"198 -1"594 0-8 7"744 4"451 3"354 1"160 -1-657 J.2.114 .6 0..2"766 .610 .623 -5.e.594 -5.037 -4"063 -4.3.026 -4.2"733 .122 0"666 -0'229 4"283 1"978 1"219 -0"283 7"750 4-433 3"332 1. p* 0"4 T* ~ 2-00 1"50 1"00 oo 2.624 LEXP -2. PERTURBATION THEORY CALCULATIONS O n e m e t h o d w h i c h h a s b e e n a p p l i e d w i t h g r e a t s u c c e s s i n t h e t h e o r y of d e n s e f l u i d s is t o e x p a n d g ( r ) i n a p e r t u r b a t i o n s e r i e s : g(r) where =go(r) + ~Egl(r ) +.573 .3.5.635 -5.630 -5.145 .8/0).073 .619 0.00 1. LEXP P$ 2"481 0"943 0"422 0"645 Et 2"518 1"113 0"653 -0"244 4'283 1"977 1"219 -0'271 7"750 4.5-608 -5-611 -5.5.975 -4.00 0.. h a r d s p h e r e s ) .568 .975 -4"031 -4.039 .665 .5-622 -5.969 1"195 -0'360 7'744 4-443 3'340 1'129 -1"722 Et 2"518 1"114 0'657 -0"228 4'283 1"978 1"222 -0"259 7'750 4"446 3"355 1"190 -1"544 EXP P~ 2"518 1"121 0'660 -0"258 4"283 1.050 .975 -4.5-611 -5.651 -5.00 ~ 2.562 P~ 2"518 1"093 0"609 -0"388 4'283 1.030 -4-051 -4.l ' 8 / a ) .5.692 EXP -2"495 -2-592 .5.2"832 .2.2.594 .495 -2"586 .00 1.5.226 -0"281 7-750 4'459 3"368 1"195 -1"582 2"518 1. Henderson et al.616 -5.2"622 .125 .610 -5.017 -4. (6) go(r) is t h e r a d i a l d i s t r i b u t i o n o f t h e S y s t e m w h e n / 3 c = 0 (i.2"658 .056 -4.602 .573 .672 -2'495 -2'583 .3.50 1.058 -4.70 Values of MC U~IN~ for Pert the Yukawa fluid ( A = 1.629 -5.995 -4. Calculated f r o m p r e s s u r e equation.Calculated f r o m e n e r g y equation.5.605 -5..975 -4.573 .3.598 -5.137 -1"668 0"6 Downloaded by [Joh Gutenberg Universitaet] at 05:46 12 April 2012 4"091 1"594 0"760 -0"911 7"001 3.626 .50 1.006 -4.985 1"224 -0"289 GMSA~ 2'518 1"122 0"655 p* 0'4 T* oo 2"00 1"50 1"00 oo 2"00 1"50 1"00 ov 2"00 1"50 1"00 0"70 MC 2"52 1"08 0"69 -0"21 4'22 2"04 1"21 -0"27 7"65 4"27 3"31 1"29 -1"63 Pert 2"518 1"123 0"664 0"246 4"283 1"985 1.2"638 .2. MSA -2"513 -2.5.446 3"353 1"185 -1.5-589 -5.8 3. Values of D.572 .625 -5.2.

where A 0 is the hard-sphere free energy.0116 0.0168 -0.0041 -0.0390 0.0016 0.+ e (1 (8) Table 4..0061 0"0046 0"0079 r*/p* 1"0000 1"0512 1"1158 1"1769 1"2349 1.0238 0.0.0 ' 0 1 7 9 -0"0219 .0363 -0. T h e f i r s t .4440 1.2903 1"3435 1"3946 1.0 ' 0 4 8 4 .0005 0-0003 -0"0013 0"0050 0.0051 0.0 ' 0 0 9 3 -0"0346 0"0064 -0"0139 0"0024 -0"0019 0'0058 0"0215 0"0118 0"0119 0'0057 0"0198 0"0203 0"0249 0"0204 0"0346 0"0308 0"0352 0"0361 0"0468 0"0417 0"0242 0"0354 0'0451 0"0294 0"0321 0-0307 0"0408 0"0107 0'0178 0.0007 0"0016 0"0034 0"0100 0"0193 0"0184 0"0182 0"0184 0"0089 0"0176 0"0176 0"0227 0"0131 0"0016 0.0154 0"4338 0"3735 0-2483 0-1508 0"0845 0"0287 0"0018 -0"0253 -0"0552 .0166 0.. T h e r e s u l t i n g v a l u e s of gl(r).0168 0"0132 0"0043 0-0025 0"0025 .0119 0.2636 0"0266 -0'0075 -0"0027 -0"0147 -0"0192 -0"0122 -0"0138 -0'0110 -0-0102 -0"0060 -0"0038 0.0314 -0"0119 -0"0151 -0-0139 -0.0555 -0"0459 -0'0447 -0.0243 0"0255 0.o r d e r t e r m . which is taken to be (7) Downloaded by [Joh Gutenberg Universitaet] at 05:46 12 April 2012 A o / N k T .0045 0.0110 -0'0082 0.0827 -0"0781 -0"0515 -0"0563 -0'0389 -0"0277 -0"0123 0"0118 0'0102 0"0199 0"0175 0. w h i c h are e x a c t a p a r t f r o m t h e s t a t i s t i c a l u n c e r t a i n t i e s of t h e M C m e t h o d .0245 0. are l i s t e d in t a b l e 4.1417 0"0369 -0"0353 -0"0449 -0"0839 -0"0744 -0.5000 0"5113 0"3253 0. can b e c a l c u l a t e d f r o m t h e c o n v e n i e n t e x p r e s s i o n s ( e q u a t i o n s (59) a n d (66) of r e f e r e n c e [16]) of B a r k e r a n d H e n d e r s o n ..0118 0.0 ' 0 7 3 9 -0"0557 -0"0609 -0"0633 -0"0760 -0"0550 -0"0573 -0"0145 -0"0622 -0-0262 -0"0401 .0196 0.0426 -0"0628 -0"0780 -0-0737 -0.0"0244 0"0335 0"3000 0"6834 0"4509 0"3312 0"1962 0'1197 0"0544 -0"0538 -0"0326 -0. T h e p e r t u r b a t i o n e x p a n s i o n of 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 c a n b e o b t a i n e d from A / N k T = A o / N k Y + / 3 ~ A 1 / N k T + (/%)~ & / N k Y + . _ l .0051 0-0363 0.0175 -0. gl(r). V a l u e s f o r g l ( r ) f o r a h i g h d e n s i t y a r e p l o t t e d in f i g u r e 1.4 .r3rfl) ideal gas t e r m s .0046 0"0133 0"0310 0.0342 0"0433 0"0446 0-0367 0"0526 0"0473 0"0486 0"0354 0"0443 0.0171 -0.0094 0"0042 0"0124 0.0256 0'6000 0"7000 0"8000 0"3178 0-0733 -0"0138 -0"0244 -0"0272 -0"0156 -0"0199 -0"0216 -0"0210 -0.Equation o[ state 245 w h i c h has a l r e a d y b e e n t a b u l a t e d [15.4916 1"5379 1"5827 1"6263 1"6688 1"7103 1"7507 1-7903 1-8289 1"8668 1"9039 1"9404 1"976t 2"0112 2"0457 2"0797 2"1131 2"1459 2-1783 2"2102 2"2417 0"2000 0-7809 0-6284 0"4162 0"3111 0"2098 0'1193 0"0815 0"0682 0"0127 0-0186 0"0081 0"0435 0-0040 -0"0212 -0"0534 -0"0131 -0"0105 -0"0091 -0-0241 -0"0126 0"0130 0"0221 0"0149 0"0261 0"0022 0"0020 0"0240 0"0236 .0265 0"0481 0"0399 0-0203 0"0313 0"0371 0"0152 0"0280 0.9000 0.0699 -0.0365 -0"0557 -0"0587 -0"0611 -0"0640 -0"0346 -0"0304 -0"0203 -0"0224 -0"0225 -0"0026 -0-0043 -0. 16]. Values of gl(r)for the Yukawa fluid ( ~ = 1-8/~).0077 0"0107 0"0056 0"0166 0"0027 0"0084 0"0006 . 0"4000 0"5939 0"4194 0"2266 0"1307 0"0191 -0.

(9) where w*(r)=w(r)/e.1 Downloaded by [Joh Gutenberg Universitaet] at 05:46 12 April 2012 1.0'1155351900 T h e An. For example. T h e values of these coefficients for the Yukawa fluid are given in table 5. H e n d e r s o n et al. However.a~P*/fl~} + PnP* + Qn(P*) ~. where p * = paa. T h e resulting values have been fitted to the function (10) An/Nk T= Cn{1 . T h e remaining coefficients are chosen by a least-squares criterion. We choose fin = ~/2 and force Pn to give the correct contribution in order p. Values of A~/NkT are plotted in figure 2. If this route is taken. The curves give the results of MSA and its generalizations. T h e other thermodynamic properties can be obtained from equation (7) by differentiation. T h e perturbation terms.8 EXP& LEXP 0.0 1. T h e final values of A 1 and A s are residues resulting from cancellation among the terms in (10).anP*/(fi~ .8 Figure 1. this pressure equation route is unattractive for .2 I F I I ~/ p*=0. for n = 1 and 2. T h e above expressions result from an integration of the Carnahan and Starling [18] hard-sphere equation of state. and thus the p~.1'1397603697 .2 1.exp [ . Table 5.3 -~ 0. are obtained f r o m An 1 -N-k-T+~n o I w*(r)g~_l(r) dr. n Coefficients in fit of A1 and A2for the Yukawa fluid (~= 1. Therefore.8/a) =n Ca Pn On 1 2 4"75 11"25 0'3150374415 -0"1401430397 . the coefficients are given to high accuracy.5"3886151999 -0"8639815240 . 0.4 0.246 D. the p~ depend on gn(a+).4 r/o 1. Values for gl(r) for the Yukawa fluid ()~= l'8/a) at a high density. the p~ can also be calculated from the pressure equation. T h e points give the perturbation theory results which are calculated by MC techniques from exact expressions. the nth-order term in a perturbation expansion of the pressure is obtained from A n by density differentiation. Since the gn(a +) are difficult to calculate by direct simulation. A x and A 2. are functionals of gn_l(r). calculated f r o m equation (9).6 1.P*)] . Pn.

We have not distinguished whether the perturbation theory values of pV/NkT come from the pressure equation or the energy equation since. Thus.04 \ \ .. respectively. n=O (12) are compared with the M C values in table 1 and the perturbation theory values of pV/NkT and Ui/N~ are Compared with M C values in tables 2 and 3. calculation of thep~.02 mA. / /" /// EXP & LEXP 0..4 / // .">*/ // / 0. p• g~(a+) p* g~(a+) 0"2 0"3 0-4 0"5 0"34 0"25 0"19 0"14 0. The points give the perturbation theory results which are calculated by MC techniques from exact expressions.Equation of state 247 0. Values of A2 for the Yukawa fluid (A= 1"8/o).0 Figure 2. The solid curve is a least-squares fit of the MC points and the broken curves give the results of the MSA and its generalizations. calculated from 2 g(cr+)= y~ (~)ngn(~+).6 0.) + /2rrp *\-1 (pnV/NkT)+ ~ (l+Zx) exp[-A(x-1)lgn-l(x)xdx' (11) 1 T h e resulting values of gl(e +) where p. and g~(~+) are given in tables 4 and 6." .0 p* 0./ // / j" / 0." < 0. the procedure may be inverted to give a method of calculation of the g~(e+). .7 0"8 0.06 ~. g~(e ) = ~ .9 0"10 0"07 0. Values of g~(o+) for the Yukawa fluid (A= 1"8/o). the two equations .08 Downloaded by [Joh Gutenberg Universitaet] at 05:46 12 April 2012 0.8 1.6 0.05 0"03 The perturbation theory value of g(cr+). However. if equation (12)is used for g(~+) and equation (6) is used for g(r).2 0. Table 6..00 0.~ is obtained by differentiating A s.f .

GMSA p*= 0.403 0"588 .0.130 .0..600 . "\~ Ms2".248 D.0"132 .10 .8/0) (perfect gas terms not included).042 0.2.4"695 0"6 0-8 . 0* 0-4 LEXP 1.1 "962 3"403 0"613 .15 F i g u r e 3.. since the perturbation theory e q u a t i o n of s t a t e is s e e n to b e g o o d i n t a b l e 2 a n d f i g u r e 4.025 .05 J r/e I 1.00 oo 2"00 1"50 1"00 oo 2"00 1-50 1"00 0"70 Pert 1"130 . give identical results.~.2"247 .o .631 .0"354 . w e g i v e t h e p e r t u r b a t i o n t h e o r y v a l u e s of t h e f r e e e n e r g y in t a b l e 7. ". T h e r e are no MC values for comparison. EXP Downloaded by [Joh Gutenberg Universitaet] at 05:46 12 April 2012 L .0. ~..8 ~ = 1.1"493 2"042 0.653 .569 .e s p e c i a l l y at high densities where the perturbation series converges rapidly. I n a s m u c h as o u r m a i n i n t e r e s t is i n t h e i n t e r r a c i a l r e g i o n s of t h e Y u k a w a f l u i d ..334 ... T h e points give the M C results and the curves give the results of various approximate theories. T* oo 2"00 1"50 1. Henderson [ [ et al.206 4-164 T a b l e 7.1 "485 2"042 0-026 . " ~ Pert/v\~.. 1. \ .. Values of A/NkT for the Yukawa fluid (A = 1.. I n a d d i t i o n .2.0"620 .1"422 2"042 0"048 .2.0.039 .403 0.0"559 . p e r t u r b a t i o n t h e o r y v a l u e s of g(r) a n d p V / N k T a r e p l o t t e d in f i g u r e s 3 a n d 4.~.246 4.~x.1 "976 3.130 .150 ...x~ !~.0"151 ..139 .0.2"027 3"403 0.443 2. However.0"355 . T h e a g r e e m e n t w i t h t h e m a c h i n e s i m u l a t i o n s is g o o d .0"654 .024 3.4-586 MSA 1. Radial distribution function of the Yukawa fluid (A = 1"8/o).0-318 .0.130 .1.692 EXP 1.588 -.2"183 .859 .0 I 1.0"590 .. it is r e a s o n a b l e t o b e l i e v e t h a t t h e p e r t u r b a t i o n t h e o r y v a l u e s f o r A a r e a c c u r a t e .0.

Density and pressure of the Yukawa fluid (h=l.0 0. . The perturbation theory values of PL* and p* are given in table 8 for T*=0.8375 ~ 0"006 0. lnp* = i n T * . The situation should be even more favourable here because 3 2 is smaller relative to A 1 than is the case for the Lennard-Jones fluid.8/a). Table 8.8. the vapour pressure can be calculated easily at low temperatures where the vapour has a vanishingly small density.8327 0"0059 0. f ~ I p I 0.4 p~ 0. ICalculated f r o m pressure equation. (13) where p*=paS/E and T*=kT/E.8336 N 0"006 a Calculated f r o m energy equation. the free energy of the liquid A L will be roughly constant in the neighbourhood of PL. Adams [19] has made computer simulation studies of the vapour pressure of the Lennard-Jones fluid and has found that perturbation theory gives accurate values of the vapour pressure of a fluid near its triple point. Downloaded by [Joh Gutenberg Universitaet] at 05:46 12 April 2012 / 2 I .1 +AL/NkT . Pert Exp(E)t Exp(P)~ GMSA(P)J~ pL* p* 0. need not be known exactly before the vapour pressure is calculated. The density of the liquid. T h e points are the M C values and the curves gives the perturbation theory results.Equation of state 249 z2 > Q. Equation of state of the Yukawa fluid ( t = 1. Recently.6 0.8335 0"0065 0. Once the free energy is known. We expect that these values are quite reliable. PL. Since the vapour pressure is small.8/a) in equilibrium with its vapour at T * = 0 " 8 .8 Figure 4.2 0. Assuming the vapour to be ideal. Presumably this means that perturbation theory is even more rapidly convergent for the Yukawa fluid (with A= l'8/a) than for the Lennard-Jones fluid.

MEAN SPHERICAL APPROXIMATION As mentioned previously.250 Table 9. The contact value is much too low.Calculated from compressibility equation. . Values of critical constants for the Yukawa fluid (A = l'8/a).2 U U N k T .pg(k)" (14) Thus. Given A and fiE. Since the convergence of perturbation theory is slower at low densities. and y. Because of the OZ equation h(k) g(k) 1 . the four parameters a=fi~p/~p. This is seen further in table 1. D. c(r) can be determined. they appear as equations (6)-(8) and (10)-(12) in reference [7]. v. the errors should not be large.31 0. 4. however.8 for all values of T* and p* which are of interest. can be determined analytically. b.g ( k ) and /~0(k)-g0(k).g(k). v ~ . Calculated from pressure equation. the Fourier transform. b. g(k).) These factors. particularly if only the difference between h ( k ) . The resulting values of g(r) at fie= 1 and p*=0-8 are plotted in figure 3. Once a. again by iteration. b. These equations are not written out fully in reference [2J. a. there are undoubtedly some errors in these perturbation theory estimates. We have compared the exact values of these parameters with those obtained from the inverse temperature expansions given by Henderson et al. Downloaded by [Joh Gutenberg Universitaet] at 05:46 12 April 2012 Finally. (It is to be noted. from the equations of Hoye and Stell [8]. five terms in a temperature expansion are sufficient for convergence in the MSA for A= 1. However. Because h(r)-c(r) is continuous. the expansion is the easiest method of calculating these parameters. the MSA for the Yukawa fluid is obtained by combining equations (4) and (5). However. and y have been determined. and y=g(a +) needed for the calculation of the MSA c(r) can be obtained by iteration from Waisman's equations. When convergent. for completeness the perturbation theory estimates of the critical constants of the Yukawa fluid are given in table 9.28 0"141 0"39-0"40 PeVe/NkTe ]. [7] and have found nearly perfect agreement. all that remains in t h e determination of g(r)= 1 +h(r) is the numerical transformation of h(k). this can be done very accurately by transforming only h(k) . can also be determined. Evidently. that a rather obvious additive factor of unity is missing from the second half of equation (8) of reference [7]. v. is transformed numerically. Henderson et al. GMSA Pert To* pc* Pc* 1"255 0"31 0"148 0"38 Ct 1"255 0. There are no machine simulation values for comparison. the hard-sphere or infinite temperature result. From this.148 0"38 P~ 1"29 0"27-0.

[7] have calculated the M S A values for gl(r). as is seen in figure 2. The MSA values for the free energy. r>cr. and p which are calculated from the energy equation are in good agreement with the MC and perturbation theory results. as is seen from table 2. [23] have proposed the optimized random-phase approximation (ORPA) which consists in replacing equation (4) by c(r)=co(r)-fiw(r). since the integration and the subsequent differentiation must be done numerically. Their values are plotted in figure 1 for p* = 0. Thus. If equation (16) is combined with the exact condition h(r)= . obtained in this manner. for the particular case of the MSA. (15) This remarkable result permits the calculation of the MSA energy equation of state with no more difficulty than that required from the pressure equation.2 U J N k T . i. calculated from (15). are tabulated in table 7. it is not surprising that the MSA g(r) is also too small at contact. The MSA go(r) is identical with the Percus-Yevick [21. Henderson et al. 22] results for hard spheres. 5. The terms in the perturbation expansion of the free energy are related to the gn(r) by equation (9). calculated from the pressure equation. The M S A values of p V / N k T . from a. a. The errors in the M S A go(r) do not result in serious errors in the MSA A 1. The M S A values of U o A. the small values of the M S A gl(r) do result in significant relative errors in A 2. However. the OZ equation can be .8. This has not been done because it requires a numerical integration which is inconvenient at high temperatures and which is not possible at temperatures below the critical temperature.1 . In most applications the equation of state obtained by differentiating these energy equation values of the free energy are more accurate than those obtained from either the pressure equation or the compressibility. The equation of state can also be calculated from the compressibility equation. ar e significantly in error. LEXP A DEXP MODIFICATIONSOF THE MSA N Andersen et al. This is primarily caused by the values of the M S A g(cr+). Normally this is a cumbersome method of obtaining the equation of state. (16) where Co(r) is the exact hard-sphere direct correlation function. the absolute error in the free energy itself is small. The free energy can be obtained from these values of U i by numerical integration (analytical integration if the temperature expansion is used).Equation of state 251 The thermodynamic properties can be calculated from the energy equation. Hoye and Stell [20] have shown that the energy equation of state can be calculated from Downloaded by [Joh Gutenberg Universitaet] at 05:46 12 April 2012 p Z = P~ NkT NkT +3 P*tg~(cr+)-g~ 2~r p*fi" J 1 ~w* g(x)x ~ dx. In fact the integral which appears in (15) is exactly the integral appearing in the pressure equation. However. However. On the other hand. or equivalently from v = .e. r < a. the M S A values of p. are listed in table 2. Both go(r) and gl(r) are too small at contact. These values of UJNE are listed in table 3.

is plotted in figure 1. Indeed the perturbation theory results. The result for g(r) can be written as (17) solved and g(r) can be calculated. therefore. if (18) is used. Since at high densities the differences in the EXP pressure and energy equations of state are similar in magnitude to the differences between the EXP and perturbation theory equations of state and since these latter differences did not result in significant differences in p*. .252 D. [23] have proposed the E X P (exponential) approximation g(r) =go(r) exp [(gL(r)] and the L E X P (linearized exponential) approximation (19) g(r)=go(r)El+~L(r)]. it is surprising to note that the L E X P and EXP A 2 is. we have assumed the EXP pressure equation vapour pressure is about the same as the EXP energy equation value (this is equivalent to assuming that the EXP pressure equation free energy is about the same as the EXP energy equation result) and have calculated the corresponding value of p* using the pressure equation. go(r) times the MSA gl(r). It must. Both are improvements over the MSA results. would improve if a larger value of gl(a +) and A s were used. g(r) =go(r) + CgL(r). 8 are given in table 8. The EXP results are especially good and are somewhat better than the perturbation theory results. g(a+) will still be small. somewhat worse than the M S A result. Henderson et al. result from compensations in higher-order terms. Although g0(a +) is given correctly in the ORPA. where higher-order terms are neglected. (18) Downloaded by [Joh Gutenberg Universitaet] at 05:46 12 April 2012 This means that the ORPA shares many of the deficiencies of the MSA. The EXP values of the density and pressure of the Yukawa fluid in equilibrium with its vapour at T * = 0 . It is seen that the small differences in the perturbation and EXP free energies (calculated from the energy equation) do not result in significant differences in p* and p*. or. which is go(r) times the ORPA gl(r). This is so despite the fact that the EXP results for gl@ +) and ~/2 are too large in magnitude. where go(r) is the exact hard-sphere RDF. ~L(r) may be approximated by the difference of the M S A g(r) and the MSA go(r) : ~L(r) ~ g~SA(r) -. There is a significant improvement over the M S A values. [24] for the square-well potential show that only the hardsphere part of g(r) is significantly affected by the replacement of (4) by (16). In fact the recent calculations of Henderson et al. The ORPA is similar to the MSA. The L E X P and EXP gl(r). Andersen et al. as is seen from figure 2. gt(r). On the other hand. The value is given in table 8 also. The LEXP and EXP approximation results [again calculating using (18)] are given in tables 1-3 and 7 and in figure 3. calculated from equation (18). In other words. Both approximations yield a first-order term. (20) where go(r) in equations (19) and (20) is the exact hard-sphere RDF.goMSA(r).

we must know the equation of state before we can use the Hoye-Stell procedure. On the other hand. Temperature variation of K in the MSA and GMSA. To calculate g(a+).Equation of state 6. we could require that the pressure and energy equations of state be consistent. we obtain g(a+) =go(a+) + 89 [g0MSA(a+)]2}. respectively. The solid and broken lines give the GMSA and MSA results. However.0 0.5 Figure 5.0 1. we now know the Yukawa fluid equation of state rather well. Thus if we neglect the change in the energy equation of state and the change in the integrals in the pressure and energy equations in passing from the MSA to the GMSA. . or at least nearly so. The advantage of the GMSA over the EXP modification of the MSA is that the analytic expression for c(r) is retained. The values of g(a +) calculated from equation (21) are listed in table 1. and MSA calculations reported earlier in this paper. (21) In where g0(a +) is the exact hard-sphere RDF obtained from MC results. However. which are used in the MSA. p0 * . K = fie and z = A. The most convenient procedure is to use the Hoye-Stell equations [8] which give K and z explicitly as functions of a=fi~p/~p and y=g(a+). this is no problem because as a result of the MC. They are somewhat inferior to those obtained from the EXP approximation. use of equation (15) should result in near self-consistency. GENERALIZEDMEANSPHERICALAPPROXIMATION 253 Downloaded by [Joh Gutenberg Universitaet] at 05:46 12 April 2012 A final procedure which we examine here is the GMSA where we assume that c(r) has the form given by equation (2) but do not make the identifications. principle. Because of this we use the EXP values of g(a +) in this work. perturbation. =8 / v / 0. it is awkward to do so because equation (15) is valid only in the MSA. If we wishes to compute c(r) in the EXP approximation we would have to compute first g(r) (ultimately from a numerical Fourier transformation) and then compute the EXP c(r) by further numerical Fourier transformation with possible loss of accuracy. However.5 #e 1. equation (21) could be generalized into an iterative procedure whereby the pressure and energy equations of state could be made fully self-consistent. We have seen that the MSA energy equations of state is very accurate.

by Henderson and Blum [5].254 D. The GMSA pressure equation estimate the pressure and density of the Yukawa fluid in equilibrium with its vapour are given in table 8.8 O Downloaded by [Joh Gutenberg Universitaet] at 05:46 12 April 2012 0. The GMSA critical point results are given in table 9. same meaning as in figure 5. LEXP. On the other hand. As fie increases. Now that a and y are determined. Since the perturbation theory and MSA energy equation of state results are so similar it is equivalent.0 1. for fiE=0. and EXP energy equations of state already reported here. This should be a very good approximation. On the other hand. but more convenient.8 in figures 5 and 6. . the GMSA pressure equation of state is slightly better than the EXP pressure equation of state.5 1. K and z can be determined from the Hoye-Stell procedure. as this would require extensive calculations and presumably would result in values which are much the same as the perturbation theory. The GMSA compressibility equation results will be identical to the perturbation theory results because of our procedure for choosing a. Again we have assumed that the GMSA pressure equation of state value of the free energy is about the same as the perturbation theory or EXP energy equation of state values. The temperature dependence of K and z are given for p*=0. The GMSA pressure equation results are very similar. The temperature dependence of K and z is qualitatively similar at other densities. z decreases towards the MSA values as fie increases.5 Figure 6. since the perturbation theory equation of state is analytic. The resulting values of K and z have been given. The curves have the We can calculate a by differentiating the MSA energy equation of state. to differentiate the perturbation theory pressures. Presumably the GMSA energy equation results would also be very similar. Temperature variation of z in the MSA and GMSA. The GMSA results are given in tables 1-3 and in figure 3. K increases in an approximately linear fashion.0 0. We have not calculated the energy equation of state. Henderson et al. I I ' o p*=0.

8/~. A. p... R.. statist.N..D.. Rev.. and BARKER. 399.J. Molec..).. and J. Phys. Phys... J. 647. 45. G. ft. D. 1977.. In addition. Molec.J.J... 1. Phys. L..D..... chem. Rev.. Chem. and BEUM. ABRAHAM. 31. HENDERSON. 19. 1977..E...W. Perturbation theory works well. A. 195.. and HENDERSON. Phys. J.. Benjamin. chem. 40. Molec.D. S. SMITH. 34. and TACO.J. Of these the G M S A has the great advantage of giving analytic expressions for most quantities of interest. 587.D. 1964. 1974.. SMITH. 1970. 411. 1966.D. ADAMS. Rev. F. G.. D. F. Phys. 209. Phys. A. Phys. Molec. 1976.. Phys. S. K. J. BARKER.. 1976. HENDERSON... 1976. rood. G. Phys. 635. chem. chem. 1291. Phys. Phys. K.J. 11-32... 32. R. 144. Phys. of the Yukawa tail is 1.J. 1977. G. WAISMAN.. statist. HovE. J.. Y. 1976. and HENDERSON.. ft. ff.. HENDERSON. 1373. p. 110. Equilibrium Theory of Classical Fluids. HovE. 67.. S. 1976. 1976. 187. 251. and FITTS.D...J. Phys. 1976.. 21. 32..K. perturbation theory and the mean spherical approximation are applied to this system. BARKER.D.. ANDERSEN. 1972.E. 64. Frisch. modifications of the M S A which do give satisfactory results are considered.J.. However.. BARKER. chem. and STELE.. S. and HENDERSON. STELE. 32. chem. STEEL. G. ft. HovE. 1964. REFERENCES PERCUS. Phys. Chem.. 25. and PERCUS. ft. Molec. Phys. 439. The M S A is less satisfactory.W. HENDERSON..D. Phys. Phys. 3253.. J... Molec. Inc. WAISMAN. 1627. LEBOWITZ. Downloaded by [Joh Gutenberg Universitaet] at 05:46 12 April 2012 [1] [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] [12] [13] [14] [15] [16] [17] [18] [19] [20] [21] [22] [23] [24] ...D. C. WAISMAN. ~. 1976. and STELE. 105. and HENDERSON. J. (in the press). J.... HENDERSON. and BEUM. 1976.. L. mad WEEKS. 62.. chem. LEBOWITZ. L. A. Lebowitz. 439. HOvE.. G. SUMMARY 255 Monte Carlo results for the equation of state of a fluid with a hard core and an attractive Yukawa tail have been given for the case where the decay parameter.J.. Phys. edited by H.. HovE....H. 16. J. Phys.. G. K. J. 23.. HENDERSON. W. 61. J. MADDEN. PERCUS.D. 1973. D. Phys. 15. and STARLING... J.J.. and STELE. BLUM. and STELE. (W.E. Molec. S. 1976. and YEVICK. 1958.. and WAISMAN. G.F. Rev. S.. J. L. L. G. 32. CHANDLER. Molec. 1971.Equation of state 7. Phys. and STELE.. S. Phys.D. HovE.. L. Equilibrium Theory of Classical Fluids. Molec. 48. Phys. L. 439. 1974. Adv. G. 1976. 51. 5026. A. 11-171.. Lett. E.. 32.. E.D. A. and STELE. 4247. and LEBOWITZ. L. CARNAHAN. 1969. 514..

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