Equation of state for the Lennard-Jones fluid

Molecular dynamics calculations of the pressure and configurational energy of a Lennard-Jones fluid are reported for 108 state conditions in the density range 0·35 ≦ ρ* ≦ 1·20 and temperature range 0·5 ≦ T* ≦ 6 (where ρ* = ρσ3, T* = kT/e). Particular attention is paid to the dense fluid region (ρ* ≧ 0·9), including state conditions in the subcooled liquid region. These new simulation results for P and U are combined with those of previous workers, together with low density values calculated from the virial series and values of the second virial coefficients themselves, to derive an equation of state for the Lennard-Jones fluid that is valid over a wide range of temperatures and densities. The equation of state used is a modified Benedict-Webb-Rubin equation having 33 constants. It fits the data well over the density range 0 ≦ ρ* ≦ 1·2 and for T* values ranging from 0·5 to 6·0 (the exact temperature range depending to some extent on the density considered). We also calculate for the same range of state con...

[1]  J. A. Barker,et al.  Fifth Virial Coefficients , 1966 .

[2]  L. Verlet.  Computer "Experiments" on Classical Fluids. II. Equilibrium Correlation Functions , 1968 .

[3]  L. Verlet.  Computer "Experiments" on Classical Fluids. I. Thermodynamical Properties of Lennard-Jones Molecules , 1967 .

[4]  K. Gubbins,et al.  Thermodynamics of polyatomic fluid mixtures—I theory , 1978 .

[5]  T. Boublı́k.  Progress in statistical thermodynamics applied to fluid phase , 1977 .

[6]  D. W. Scott,et al.  Experimental thermodynamics of non-reacting fluids , 1975 .

[7]  M. S. Ananth,et al.  Perturbation theory for equilibrium properties of molecular fluids , 1974 .

[8]  G. N. Patey,et al.  The free energy of spheres with dipoles: Monte Carlo with multistage sampling , 1973 .

[9]  R. D. Mccarty,et al.  A modified Benedict-Webb-Rubin equation of state for methane using recent experimental data , 1974 .

[10]  K. Gubbins,et al.  Perturbation theory for molecular fluids: Third‐order term in the Pople expansion , 1978 .

[11]  E. Bender.  An equation of state for predicting vapour-liquid equilibria of the system N2ArO2 , 1973 .

[12]  J. McTague,et al.  Crystal nucleation in a three‐dimensional Lennard‐Jones system: A molecular dynamics study , 1976 .

[13]  K. Gubbins,et al.  Thermodynamics of mixtures of nonspherical molecules. III. Fluid phase equilibria and critical loci , 1976 .

[14]  Jean-Pierre Hansen,et al.  Phase Transition of the Lennard-Jones System. II. High-Temperature Limit , 1970 .

[15]  I. R. Mcdonald.  Application of thermodynamic perturbation theory to polar and polarizable fluids , 1974 .

[16]  K. Gubbins,et al.  Monte Carlo study of perturbation theory for the radial distribution function , 1973 .

[17]  J. Pople.  The statistical mechanics of assemblies of axially symmetric molecules - I. General theory , 1954, Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences.

[18]  J. G. Hust,et al.  Curve-fitting techniques and applications to thermodynamics , 1967 .

[19]  D. J. Adams,et al.  Calculating the high-temperature vapour line by Monte Carlo , 1976 .

[20]  A. Buckingham.  Molecular structure and properties , 1975 .

[21]  W. G. Madden,et al.  Perturbation theory for the radial distribution function for simple polar fluids , 1974 .

[22]  D. Henderson.  Exact and approximate values for the radial distribution function at low densities for the 6:12 potential , 1965 .

[23]  K. Gubbins,et al.  Liquids of Linear Molecules: Computer Simulations and Theory , 1977 .

[24]  L. Verlet,et al.  Perturbation theories for polar fluids , 1974 .

[25]  Jean-Pierre Hansen,et al.  Phase Transitions of the Lennard-Jones System , 1969 .

[26]  G. S. Rushbrooke,et al.  Theory of polar liquids , 1973 .

[27]  J. Murrell,et al.  Molecular dynamics and chemical reactivity , 1977 .

[28]  I. R. Mcdonald,et al.  An equation of state for simple liquids , 1972 .

[29]  L. Verlet,et al.  Perturbation Theory and Equation of State for Fluids , 1969 .

[30]  D. Tildesley,et al.  Multiple time-step methods in molecular dynamics , 1978 .

[31]  J. Rasaiah,et al.  Thermodynamic perturbation theory for simple polar fluids. II , 1972 .

[32]  J. Perram,et al.  A new expansion in the theory of polar liquids , 1972 .

[33]  J. Barker,et al.  What is "liquid"? Understanding the states of matter , 1976 .

[34]  M. E. Rose.  Elementary Theory of Angular Momentum , 1957 .

[35]  K. Gubbins,et al.  Thermodynamics of mixtures of non-spherical molecules , 1975 .

[36]  D. J. Adams,et al.  Grand canonical ensemble Monte Carlo for a Lennard-Jones fluid , 1975 .