PHYSICAL REVIEW VoLumE 159, NUMBER 5 sULY 1967 Computer “Experiments” on Classical Fluids. I. Thermodynamical Properties of Lennard-Jones Molecules* Loe Venues Belfer Graduate Schl of Sconce, Yeshiva Univesity, New Vork, New Vork (Received 30 January 1967) ‘The equation of motion of a system of 864 particles interact ous values ofthe temperature and density, Deen integrated for csqltrium properties have been ealeulated and through a Lennard-Jones potentia! has lative, generally, toa fad state. The ‘shown to agree very well with the corresponding properties of argon. Its concluded that, to a good approsimation, the equiibium state of argon ean be Seseribed through a two-body potential I. INTRODUCTION HE “exact” machine computations relative to classical fhuids have several aims: Tt is possible to realize “experiments” in which the intermolecular forces are known; approximative theories can thus be unambiguously tested and some guidelines are provided to build such theories whenever they do not exist. The comparison of the results of such computations with real experiments is the best way to obtain insight into the interaction between molecules in the high-density states. ‘The Monte Carlo method initiated by the Las Alamos ‘group! is a frst example of these “exact” methods. It amounts to a direct computation of the integrals in- ‘volved in the canonical averages, Ttis easy to carry out, with the inconvenience, however, of providing no information on the time properties of the system. ‘The dynamics of an isolated system can also be considered and used to calculate time averages and time-dependent properties. The case of hard spheres ‘and hard spheres surrounded by a square well has been extensively studied by Alder e al? In the case ofa two- body interaction simulating more closely the interaction between the molecules, itis possible to integrate directly the equation of the’ motions of about a thousand pactcls, as brilliantly demonstrated by Rahman? The present paper presents some of the results which have been obtained, using a technique inspired by Rahman's work, fora system of 864 particles interacting through ‘a Lennard-Jones potential In Sec. IK we give some technical details on the method which we uses in particular, we describe a book- keeping device that cuts the computing time by a factor of the order of 10. In Sec. IIL we give and discuss the results obtained for the pressure, the internal energy, the high-frequency elastic moduli, and the sotopic separation factor. These * Supported by the U.S. Ait Force Ofice of Scientiie Research Geant No. £0866 ‘TPermanent address: Faculté des Sciences, Laborataie de hysiaue Thcorque et Hautes Energies Batiment 211, 91-Orem PEW Mod tn Bae, Chem, Poe 2, 20095 388 J Alder and T. E- Wainwaight, J. Chem Phys, 33, 1499, aoe)? TA, Rahman, Phys, Rey. 136, A405 (194). 159 results, summarized in Table Tare sufciently numerous to allow a comparison on the whole density range of the fuid state and on a wide temperature range which essentially excludes the extremely high temperatures. ‘The overall agreement is surprisingly good. It appears thatthe many-body forces, if they are at all important, Jbehave so as to realize an effective interaction which i state independent to a good approximation. "The correlation functions are described and discussed in a separate paper: The formalism necessary to express the fluctuations in the microcanonical ensemble was discussed recently. It can be applied to calculate the derivatives of the thermodynamic functions (eg, the speciic heat and 4p/@p) in terms of ffuctuations averaged over time, The results are not very precise and will only be presented as an illustration of these theoretical considerations. ‘The results on the time-dependent properties wil be reported later. Il, DESCRIPTION OF THE COMPUTER EXPERIMENTS We consider a system of 864 particles, enclosed in a ‘cube of side L, with periodic boundary. conditions interacting through a two-body potential of the Lennard-Jones type V)=M(e/r)*— (6/7). @ ‘This potential is cut at r,=2.5e in most of our experi- ‘ments, oF, in some of them at r,=3.3s. The problem is to integrate the equation of motion or mE fra) @ ae We choose the following w pressed in units of ¢ (¢=3.405 A for argon), and the energies in units of ¢ (e=119.8°K for argon)? The thermodynamic quantities will thus be measured in the ‘The lengths are ex- “1, Var to be bbe). “atest ee roy Rev 16 1613 oe. 14:1 tJ Bay de Vet Pp Re 230 (8 9 Mts nd H. Wier, Physic 15, 27 198, 98159 COMPUTER ‘usual “reduced” units. The time unit is chosen so that m= 48a; it tums out to be, for argon, equal to 3X10- sec. This time is of the order of the kinetic relaxation times of the system in the ease considered in this paper. With this in mind, we have, for the force acting on particle # in the + direction, felrw=m(ea\lre*—05r7). (3) To integrate (2), we use the very simple algorithm. NUE =—n(—MAANOFE tly, 8) where his the time increment which we take equal to 0.032. This is practically the value chosen by Rahman (ie., 10- see in the case of argon). We have checked that this time increment is adequate and even super- fluously small in most cases, For instance, for T= 1.38, p=0.55 sperature just above critical, density almost twice critical), we have performed two integra- up to the time /=4, Tn one case we have taken /=0.082, in the other h=0.016, with the same initial conditions. The difference in position at time 1 is typically of the order of 0.001 and the difference in the thermodynamic quantities, at the same final time, amounts to 1/1000, In this kind of calculation, most of the time is spent in computing the force. If no special devices are introduced, we must, at each step, compute }N(V=1) terms, most of which tum out to be zero. ‘We introduce the following bookkeeping device® which ‘cats the computing time by a factor of the order of 10: Every nth step, we compute all the 4N (W—1) distances, ‘and, given a particle i, we make a table of all the particles which are within a distance rw of that particle. ‘Then, for the next n—1 steps in time, we take into account only the particles in the tables. There is no ‘error as long as ry is sufficiently larger than r. so that no particle outside the table traverses the “skin” of depth rir—r. and gets into the range r, ofthe potential ‘The feasibility of such a procedure can be easily appreciated by giving some orders of magnitude: Let 8 be the root-mean-square velocity in our units, it is typically of the order of 0.35 if this sso, no error is made as long as rere © Ii, for instance n= 16, nth= 0.15, By choosing rv=3.3, for r4=25, the condition (5) is largely met, and at the same time the ‘skin”” depth stays reasonably small. We have checked, by following some systems for several hundred steps in time, that no difference at all was observed when n was reduced. Moreover, the conserva- tion of the total energy and of the total velocity, which stays of the order of 10°, is a guarantee of the sound- ness of the whole procedure, ing tricks have been considered before: See Tov the andaphers uA, otener (New Yo University Report No, NYO-1803, igok (unpublished) “BXPERIMENTS"' ON CLASSICAL FLUIDS 99 With this device, the time spent for an integration step at the density 0.45 is about 12 secon the UNIVAC 1107 of the Faculté des Sciences, Orsay, where the fist calculations were made, and ten times less (with careful ‘machine coding of the time-consuming subroutines) on the CDC 6600 of New York University, where the sreatest part ofthe results reported here were obtained. With that machine, a typical “experiment” takes about 1h. It goes as follows: The positions are initially taken, in general, at the nodes of a face-centered-cubic Tattice which has the desired density, and the velocities are chosen at random with a Gaussian probability law, ‘Three hundred steps in time are sufficient, in general, to reach equilibrium. The computation is then carried on for 1200 steps in time (this corresponds, for argon, to 1.2X10-" see). The main part of the computation con- cems the study of equilibrium quantities (thermo- dynamic functions: temperature, pressure, internal ‘energy, specific heat, et.; time-independent correlation functions) and of nonequilibrium quantities (velocity autocorrelation function, elastic constants, viscosities, heat conductivity, et). The necessary technical details will be given when these results are reported, II THERMODYNAMIC QUANTITIES A. Temperature At each step in time the velocities are calculated simply by the formula v= [n(n i) Y2k. o ‘The temperature is, at time f, $ of the kinetic energy, in our units TH16 v/N. o ‘The error entailed by the use of (6) is of the order of 1/1000. This error is of no consequence, except that it gives rise to small irregularities in the total energy which should be otherwise strictly constant. The ‘temperature, averaged over the time, is affected by a statistical error of the order of 0,004. 3, Presure ‘The pressures cleulted from the vl theorem p14 mA pe 2. ef Bean, ar awa BEM) ear, 5k © ‘The second term of (8) is the time average of the virial. ‘The last term is a correction term which takes into account the effect on the pressure of the tail of the potential which has been neglected in the dynamics. ‘The influence on the main term of (8) of the tail of the potential, which has been neglected in the dynamics ccan be appreciated by considering that cutoff tail as a100 “Tapas I, List of themodynamial rela: » the parce dest and the temperatures /ois the compres ctor, ‘nD gs edual to (VV}/m Ke and Ge ate te inal eequeney bulk find shear modull, respectively, Ku/Oq thee tal, nd 7» the AIstance at'which’ the potential Is cut” Reduced ubitsare‘used throughout. ot Kalu te Os 1098 1st 25 Oss Ot Lie 25 Oss Oso —018 ie 25 Oss 2889 36 2bt 23 Oss 23 420 ior 25 Oss 12l4 $00 Ts 25 Oss Liz 278 1s 25 Oss O88) Tot 170 23 Das 0782 098 1g 25 Bas 0786 O99 ter 25 Oss 0700 O78 169 25 Oss O71 036 Tes 25 Oss 06s —0.20 ter 25 Os Oso —120 1sr 23, 07s 2s49 310 196 25 O73 30 Let 133 25 073 1b 090 16s 25 O78 Lon O89 165.33. 07s oss 1% 25 07s O87 138 23 06s 2857 Tks 33. Des 1385 10 25 ss 136 13s 33 Bes 900 —0% 13025 O53 ois 16 tho 25 Oia S26 186 tas 25 O36 Lab. Os) 1s 25 0326 1326 042 Tse 35 03, 138,840 1st 23 04s 462s 168 nor 23 04s 2958138 ip 33 as L7H O74 Ket 23 Os yet OF tek 3 as 170 O74 ist 2s as 1552 075 1s 2s os 142 Ot is 25 Of 1a 038 1 33 0351620 O58 rst 23 038 188 0.0 19 23 ‘weak long-range perturbation? The effect on the main term of (8) is quite small: It amounts to 0.006 in the cone ease studied (p .05). Tt is smaller than the statistical eror which is generally of the order of (0.01 when 1200 steps in time are considered. The main error comes certainly from the correction term which is very large at high density and low temperature where it is of the order of 1 for r.= 2.5 ‘The replacement of g(7) by 1 in the correction term leads, for rr=25, to an error which may reach 0.05 at the highest density and lowest temperature considered here. Such a replacement is, however, not necessary as the extrapolated values of g(7}* may be used. ‘Asa whole, we believe thatthe over-all error on p/p is probably of the order of 0.01 around the critical density and may reach 0.05 in the high-density and low-temperature region. ‘The results so far obtained have been gathered ‘Table I. Fig. 1 shows p/akY for some isochores at high Lebo (private communication). LOUP VERLET 159 ° £ t © 3 Fr, The copes facta e/a fnction of 9 for the ces SOAS 78 Bi ah 048 Go yt eo at caves ito foe gad id ot density (9=0.88, 0.85, 0.75, 0.65, and 0.45), and the comparison of the equation of state determined by var us experimental groups in Amsterdam," Toronto, and Louvain.” ‘The overall agreement between “theory” and experi- rent is surprisingly good: It appears that the Lennard- Jones potential is a quite satisfactory interaction as far as the equilibrium properties of argon are concerned. tis to be noted that if, instead of argon, xenon were chosen for the comparison, the agreement would not be s0 good. For instance, with, for T=1.35, p=0.75, the value of 8p/o from molecular dynamics is 0.86; the same quantity is equal to 0.86 in argon. For xenon (with the reduction parameters. «/l=225.3°K, o=4.07 A), the value 1.05 is obtained.!* On Fig, 2 are represented three isotherms: One at high temperature (T'=2.74) where comparison can be rade with the results obtained along time ago by Wood and Parker and also with a Lennard-Jones potential ‘through the Monte Carlo technique; the low- ‘temperature isotherm 7=1; and the isotherm 7=1.35, which is also an isotherm for which Monte Carlo com: “nya IH. Levelt, Physio 26 361 (1960, Wan, Witzaburg, Univerty of Toronto disutation (gpa copy available in Dissertation Absteats 25, 1208 (obs) [AY Van Isterbeck, O. Verbeke, and K, Staes, Physica 29, a2 (oes)159 COMPUTER Fre, 2, Forth othenge T0274, T=135, nd T= 0p scrgifags ac Te qa pagl ee Sor abahes wie hep ot he Taal Wi uate BSR nln eal ane Cass 7 Te Ta uae cern ai fs aoe 14. pputations have been made.§ That isotherm will be used. below to examine the question of the critical constants. For low values of the pressure, our computation may describe metastable states: ‘The periodic boundary prevents the occurrence of inhomogeneities of a size larger than the side of the box, so that the formation of a two-phase system is very much hindered, The low pressure part of the isochores at p=0.85 and 0.88 hhas been obtained by “cooling” a liquid configuration: ‘That is, we start from a spatial distribution relative to the liquid state, and a Gaussian initial velocity distri- bution, Equilibrium configurations corresponding to ‘supercooled liquids may thus be reached, We have also started from solid-like spatial configurations, with again Gaussian velocity distributions. The temperature To corresponding to this initial velocity is progressively raised until “melting” occurs, Our criterion" for melting. is based on the evolution in time of pe=Zscoskx,: ‘There & corresponds to the smallest vector of the reciprocal lattice, ie., = 4x/a, where @ is the side of *D, Levesque and I, Veet, Physica (o be published TE Ness Grae comedanteon” eno. “ EXPERIMENTS" ON CLASSICAL FLUIDS 101 unit cell of the original fec lattice, which, in the 2 direction extends from 0 to L. For a soli, ox is of the order of WV, Tt oscillates around 0 with an amplitude of the order of VN for a liquid, If we admit that the metastable states of the solid are short-lived (as com- pared to the total time of the computation, ie. 1,2X10™ sec for argon), we can find by trial and error the melting temperature. For p=0.85 a solid configura- tion is still observed for T=0.695, It corresponds to value of the initial temperature 7o=1.308, For Ty=1.366, melting does occur. Experimentally (see Fig. 1) melting occurs at T=0.704. For p=0.88, we have a solid for 1'=0.825; this corresponds to Ty= 1.545. With Ty=1.67, melting is reached. Experimentally, melting takes place for T=0.82 at that density. The agreement with experiment is seen to be good. ©. Critical Constants Because of computational errors, the precise deter- mination of the critical constants is dificult. We believe, however, that a careful examination of the data warrants the following discussion and conclusions. (a) The extrapolation of the isochores towards the critical temperature yields results which are in good agreement with the Monte Carlo results of Levesque and Verlet® (108 particles, about 300000 configura- tions). Those results, for 7= 1.35, are shown in Fig. 2 and in Table I. (0) The PY IT equation leads at p=0.45 and p=0.5 to values of/p which are definitely t0 low. The trend to give to low values for the quantities at intermediate density is already noticeable at p=0.4, as may be seen from Table IU, although one is at the border of com- putational errs, If the values yielded by the PY IT equation are corrected by 0.005 at p=0.85, and by 0.02 at p=04—and this seems to be the most that can be expected—the following critical constants are obtained: Ty= 1.32, po=0.32, and 8:fx/p.=0.3, instead of those obtained from the PY II equation, T= 1.36, p.=0.36, ‘and BPe/oc=0.36. We expect the critical constants t0 be situated somewhere between those limits, Tavs I, Values of 6p/o forthe isotherm T'= 1.38 obtained from the PY and PY Ll equations (Ref, 13), Monte Carlo com= ptations FC.) (Ref. F3), extrapolation of the, molecular Sams ACD.) ale, Stim al est 1) ade roman, and experiment on argon (Ret PY PYIL Mc. 02 0510 03. 0396 50376 Bt 0386 ass 05. 0582 092 1.256 050 036 030 027 025 0506 | oar 0.380 o3st oss oe oss oa 0508 o378 034s 0338 0389 0406 oast 0709 0.364.003 os2002 029.2002 0.30.20.02 033.2008 bazeo02 (082-50.08 0.285005 0.332.003 0.442005 0.86:£0005102 ‘Tanga TTT, Values of p/p, of the inverse compressibility i °D, and of the ineration part af the Integral ay given by 3 lecular dynamics (MED), the PY Hand the PY equation 46 pyr lp om. 26/5 O38 053 i aor 2 (©) The five viral series gives values of p/p which are clearly too high by 0015 at p=0.3, by 005 at p=0.35, and by 0.06 at p=04, The difference then ‘iminishes and changes sign at high density. The Padé approximant shows the same behavior but @ little ess accentuated, We conclude that one or several virial cocflicients after the fifth one must be negative, and that some higher ones must be positive again. ‘The critical point deduced by Barker ef al from their series is situated at T.=1.29, p.=0.26, and Bep./oo=0.35. The critical density is quite low, @ consequence of the too low pressures at intermediate densities, (@) Table IV summarizes the situation: There a comparison with experiment on argon is made, which shows that there exists a discrepancy of at least 5% on the critical temperature. This raises the following problem: Its known nowadays!" that the low-density data are not well fitted by a Lennard-Jones potential; 4 potential with a deeper bowl and a weaker til, such as the recently determined Kihara potential,” Seems ‘uch more appropriate. It would seem natural to guess that using such a potential will improve the situation in the critical region. The reverse is true: Levesque and Vieillard-Baron,4 using the PY IT equation, find 4 critical temperature of 1.42 (with the same units as before). The blame for this discrepancy may be put on ‘many-body forces, Even at density around the critical region, a relatively large amount of those forces would be needed. It appears that these many-body forces ‘Tavre IV. Celia constants obtained from the PY 1 equation (ef 1), rom the PYIT equation eamected as explained in See. TEA, rom the Stern viral series (Ret 18) and from exper ent (Rel 10) Babel tr ta 1362008 0362005 PyiL Maxim conection 1.32 030, Seemed 129 0382 Experiment 126 036 J se, etna nd A om, Chom, Boe wd daa 1B aa wd oC sein Pe Rey fz hoo SRR RST) Fula Ns, We Phys. 43, 3998 (1965); J. Rowlinson, Discussions Faraday Soc, Bp fg Me Rha Ws a Sith Pe Pi 7 9 ish Pi Levee ad J.Virol), LOUP VERLET 159, should then manifest themselves in the form of an interaction which is clearly state dependent at high density; and this seems to be contradicted by the excellence of the fit obtained in the present paper. D, Internal Energies ‘The part of the internal energy due to the intera Uéis calculated as the time average of the sum of the interparticle interaction energies. A tail correction is included, as for the pressure and the energy ; the over-all error appears to be of the order of 0.02. The agreement between our results and the (not too extensive) experi mental data” is satisfactory, although the calculated internal energies are a litle larger in magnitude than the experimental one. For instance, for p=0.45, at 985, Uaia'=—2.60, density, for T= 1.764, Unul= —2.89, Very higher ‘densities, the same trend. 's ‘noticeable, for 920.5426, T=1.404, Unie! ~3.63, Usagi=—3.55. It appears, roughly speaking, that the Lennard-Jones potential is slightly too deep. E, High-Frequency Elastic Moduli Zwanzig and Mountain have shown that in simple fluids the ininite-requency bulk modulus Kq and the infinite-fequency shear modulus Gy can be expressed jn terms of the radial distribution function; and that, furthermore, inthe case ofthe Lennard-Jones potential, the necessary integrals can be expressed in terms of the pressure and of the internal energy, so that Ge and Ky are simply given by the following expressions: Ga 3p—20T— (24/5)pU', o Ko=(8/3)Got2(p~0T). (10) Results for K, Ga, and the ratio K./Ge are given in ‘Table I. When the temperature is low, the internal- energy effects predominate and Kx/Ge is near (5/3), the value obtained from Cauchy condition for solids. ‘We may compare the “exact results” given in Table T with those obtained by Zwanzig and Mountain who ‘used (9) and (10), and the experimental data of Levelt," supposing that the interaction between argon atoms is exactly the Lennard-Jones potential. The good agree~ ment between those results and ours shows again— although this proof is not independent of the preceding ‘ones—that the Lennard-Jones potential is appropriate to describe argon in the temperature and density do- ‘main considered in the present paper. F, Isotopic Separation Factor ‘The separation faction in a liquid-ges mixture of isotopes of argon can be expressed? in terms of the rig eso a04 R,D, Mount, J Chem, ys 4, 3G Casanova, A. esi and N. Tera, Physica 30,987 (196).159 COMPUTER 2 Os t ts E Fig. $. The solid, Hines show the quantity C=0#/2zem = (8179/9649 forthe ochores p=0.85, e=0.75, nd p= 0.65, 16 1 function of Bx The eroses represeat the intercepts of those ‘Lochores wth the experimental’ liquld-gas cocristence line. It ‘shoul be compared with the lotople separation factor in argon (Wet 20 (ranges). average value of the Laplacian of the potential (V(r). ‘The quantity Q2= (1/M1)(V'V()), which is also im- portant in the time development of the system, has been calculated, and the values we obtained are shown in Table I, The quantity C=/2zp is plotted for several isochores in Fig. 3. We have used experimental EXPERIMENTS" ON CLASSICAL FLUIDS 103 information (pressure-versusdensity curve for the coexistence curve, as shown on Fig, 1), to locate the temperature of the coexistence line on the isochores. It may be seen easly, however, that this introduces very little arbitrariness. A good fit of the experiment is ob- tained, as seen from Fig. 3. IV. CONCLUSIONS We have shown, using Rahman's work as a starting point, how it is possible to integrate the equations of motion of about a thousand particles in a relatively easy way. The first application of this tool is the thermodynamic study of a fluid composed of atoms interacting through a Lennard-Jones potential. The striking result of this study is the over-all agreement between the results thus obtained and the thermo- ‘dynamics of real argon. Tt is likely that those results can still be slightly improved and that a two-body: potential can fit the experimental data with a large degree of success. ACKNOWLEDGMENTS: ‘The author is very grateful for the hospitality of ‘Yeshiva University where most of this work was done, Tt is a particular pleasure to thank Professor Joe! L. Lebowitz; numerous long discussions have been both inspiring and stimulating in the series of studies whose results we have begun to describe. We are grateful also to D. Levesque, J. Vieillard-Baron, and D. Schiff for hhelp and discussions. Last, but not least, we must acknowledge the profuse computing opportunities and the warm welcome in the Courant Institute of New ‘York University, where the largest part of the computa- tions were performed, and where the author benefitted from interesting and helpful discussions with Professor J. Percus and Dr. M. Kalos.