Determination of Intermolecular Potentials

Keller J B and Zumino B 1959 Determination of intermolecular potentials from thermodynamic data and the law of corresponding states J. Chem. Phys. 30 1351... 

F. A. Momany, G. Vanderkooi, and H. A. Scheraga, Proc. Natl. Acad. Sci., USA, 61, 429 (1968). Determination of Intermolecular Potentials from Crystal Data. I. General Theory and Application to Crystalline Benzene at Several Temperatures. 

A thorough reference work with emphasis on the determination of intermolecular potentials from experimental data. 

Progress on the Determination of Intermolecular Potential Energy Surfaces from... 

PROGRESS ON THE DETERMINATION OF INTERMOLECULAR POTENTIAL ENERGY SURFACES FROM HIGH RESOLUTION SPECTROSCOPY... 

Accurate knowledge of transport properties of pure gases and liquids, and of their mixtures, is essential for the optimum design of the different items of chemical process plants, for determination of intermolecular potential energy functions and for development of accurate theories of transport in dense fluids. A previous lUPAC volume, edited by Wakeham et al. (1991), also produced by Commission 1.2 through its Subcommittee on Transport Properties, has described experimental methods for the accurate determination of transport properties. However, it is impossible to measure these properties for all industrially important fluids, and their mixtures, at all the thermodynamic states of interest. Measurements therefore need to be supplemented by dieoretical calculations. 

Momany, F. A., Vanderkooi, G., 8c Scheraga, H. A. (1968). Determination of intermolecular potentials from crystal data. I. General theory and application to crystalline benzene at several temperatures. Proceedings o/t/ieNatiowaJ Academy o/ Sciences, 61, 429. 

U. Buck and H. Pauly, Determination of intermolecular potentials by the inversion of molecular beam scattering data. II. High resolution measurements of differential scattering cross sections and the inversion of the data for Na-Hg, J. Chem. Phys. 54 1929 (1971). 

Determination of intermolecular potentials for complex molecules with sufficient for this purpose accuracy, however, is very difficult and slow. Rowlinson (1990) states "It is salutary to remember that until about twenty years ago the accepted figure for so simple an energy of interaction as that between a pair of argon atoms was about 20% in error. Spectroscopists and workers in quantum mechanics are working on the problem for more interesting molecules but their progress is slow."... 

In the field of intermolecular forces a book has been published by Kaplan241 which provides a coverage of the theory from long-range forces (including retardation effects) to short-range forces and nonadditivity. The determination of molecular potentials from experimental data is also considered in one chapter of this book. 

The various virial coefficients can be determined from the P-V-T data for real gases. It is possible to calculate them from a knowledge of intermolecular potential energy. Unfortunately, however, this potential is not accurately known and hence the calculation of higher virial coefficients is a formidable problem in theoretical chemistry. The first virial coefficient is, evidently, equal... 

H. A. Scherage, "Intermolecular Potentials from Crystal Data III. Determination of Empirical Potentials and Application to the Packing Configurations and Lattice Energies in Crystals of Hydrocarbons, Carboxylic Acids, Amines, and Amides," Jour. Phys. Chem., 78(16), 1595 (1974). 

M. J. Sippl, G. Nemethy, and H. A. Sheraga (1984) Intermolecular potentials from crystal data. 6. Determination of empirical potentials for 0-H...O=C hydrogen bonds from packing configurations. J. Phys. Chem. 88, p. 6231... 

Elastic scattering of two atoms or molecules provides a direct method to determine the intermolecular potential between the colliding particles. It cannot compete with spectroscopy concerning the precision of the potential determined. However, the beam scattering method is in principle more universal than spectroscopy and covers the entire energy range. All other... 

If we examine the agreement between calculations, based on the various potentials, and the experimental macroscopic properties, the question of how well these properties determine the intermolecular potential must surely arise. The relationship is not simple. Minor modifications of the potential do... 

F.A. Momany, L.M. Carruthers, R.F. McGuire, and H.A. Scheraga, Intermolecular potentials from crystal data. III. Determination of empirical potentials and application to the packing configurations and lattice energies in crystals of hydrocarbons, carboxylic acids, amines, and amides. J Phys Chem 78,1595,1974. 

W e shall try to give a eursory view of the variety of intermolecular potentials in use for liquid systems, paying more attention to the simplest ones. We shall almost completely neglect potentials used in other fields, sueh as the scattering of two isolated molecules, the determination of speetroseopie properties of dimers and trimers, and the accurate study of local chemical interactions, which all require more sophisticated potentials. 

Can one determine the behavior of the time correlation functions for all times, over a wide range of densities, and for the class of intermolecular potentials considered here, as illustrated in Fig. 1 ... 

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