Triple-dipole dispersion forces in dense fluids

The contribution of triple-dipole dispersion forces to thermodynamic properties of fluid argon is determined from an analysis of computer-generated configurations of atoms. For states of liquid argon lying near the liquid-vapour equilibrium line the effect of triple-dipole interactions is to increase both internal energy and volume by several per cent. The inclusion of the triple- dipole contribution largely accounts for the discrepancies which are found between the experimental values of internal energy and pressure and the values calculated from a potential chosen to simulate the true pair potential between argon atoms. Accurate values are also obtained for the contribution of the triple-dipole potential to medium-dependent effective pair potentials of the type developed by Sinanoglu (1967). Results are given in tabular form for six states of fluid argon and for the corresponding states of krypton and xenon.

[1]  O. Sǐnanoğlu.  An intermolecular potential for use in liquids , 1967 .

[2]  L. Verlet,et al.  NOTE ON X-RAY SCATTERING BY ARGON. , 1968 .

[3]  John S. Rowlinson,et al.  Physics of simple liquids , 1968 .

[4]  O. Sǐnanoğlu,et al.  Medium‐Dependent Intermolecular Potential for Liquids and Its Use in Obtaining Free Energy and Entropy , 1968 .

[5]  R. J. Bell,et al.  The van der Waals interaction of two or three atoms , 1966 .

[6]  C. J. Pings,et al.  Structure of Liquids. IV. Direct Correlation Functions of Liquid Argon , 1967 .

[7]  Ian R. McDonald,et al.  Examination of the Adequacy of the 12–6 Potential for Liquid Argon by Means of Monte Carlo Calculations , 1969 .

[8]  W. Bade.  Drude‐Model Calculation of Dispersion Forces. III. The Fourth‐Order Contribution , 1958 .

[9]  N. Kestner,et al.  I. Studies of Cavities Containing One and Two Electrons in Metal-Ammonia Solutions. II. Accurate 'Effective' Intermolecular Pair Potentials in Gaseous Argon. , 1968 .

[10]  I. R. Mcdonald,et al.  Calculation of thermodynamic properties of liquid argon from Lennard-Jones parameters by a Monte Carlo method , 1967 .

[11]  B. M. Axilrod.  Triple‐Dipole Interaction. I. Theory , 1951 .

[12]  H. Graben,et al.  Triple-Dipole Potentials in Classical Nonpolar Fluids , 1969 .

[13]  R. H. Tredgold,et al.  RESEARCH NOTES: On the Crystal Structure of the Rare Gases , 1956 .

[14]  Y. Midzuno,et al.  Non-additive Intermolecular Potential in Gases I. van der Waals Interactions , 1956 .

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

[16]  W. Streett,et al.  Experimental Study of the Equation of State of Liquid Argon , 1969 .

[17]  J. Barker,et al.  Calculation of Gas Transport Properties and the Interaction of Argon Atoms , 1964 .

[18]  H. Margenau,et al.  Nonadditivity of Intermolecular Forces , 1967 .

[19]  I. Zucker,et al.  The effect of long-range three-body forces on the zero-point energy of the inert gas solids , 1968 .

[20]  O. Sǐnanoğlu,et al.  Effective Intermolecular Pair Potentials in Nonpolar Media , 1963 .

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

[22]  A. Michels,et al.  Isotherms of argon between 0°c and 150°c and pressures up to 2900 atmospheres , 1949 .

[23]  Edward Teller,et al.  Interaction of the van der Waals Type Between Three Atoms , 1943 .

[24]  G. S. Rushbrooke,et al.  On triplet potentials in the theory of classical fluids , 1967 .

[25]  John S. Rowlinson,et al.  Liquids and liquid mixtures , 1959 .

[26]  J. A. Barker,et al.  Three-Body Forces in Dense Systems , 1968 .

[27]  J. Barker,et al.  Atomic interactions in argon , 1968 .

[28]  J. Rowlinson.  The introduction of triplet potentials into the Percus-Yevick theory of fluids , 1967 .

[29]  J. Prausnitz,et al.  Intermolecular Potential Functions and the Second and Third Virial Coefficients , 1964 .

[30]  L. Jansen,et al.  Stability of Crystals of Rare-Gas Atoms and Alkali Halides in Terms of Three-Body Interactions. II. Alkali-Halide Crystals , 1964 .