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Basic Theory of Intermolecular Forces

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Molecular Liquids: New Perspectives in Physics and Chemistry

Part of the book series: NATO ASI Series ((ASIC,volume 379))

Abstract

A general survey of the theory of intermolecular forces is provided. The interaction energy of two atoms is assumed to depend parametrically on their separation R, and for two molecules containing N 1 and N 2 atoms the interaction energy u(R) has 3(N 1+N 2)−6 variables; thus for two diatomics there are 6 variables and for H2O---H2O there are 12. Because of this complexity, we seek simplifications. It is useful to separate u(R) into long and short-range components, where the long-range interactions are related by perturbation theory to the charge distribution and polarizabilities of the isolated monomers. The short-range forces are due to the overlap of the electron clouds of the monomers and depend upon antisymmetrization of the ‘supermolecule’ wavefunction with respect to exchange of electrons between the interacting monomers. The convergence of the multipole expansion is considered, and the importance of using ‘distributed’ multipoles and polarizabilities in evaluating molecular interactions is stressed. Vibrational contributions to interaction energies are considered, and it is shown how zero-point oscillations tend to make the deuterium bond stronger than the hydrogen bond. The effects of the solvent on the interaction energy and on the properties of dissolved molecules is briefly considered.

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Authors and Affiliations

  1. University Chemical Laboratory, Lensfield Road, Cambridge, CB2 1EW, UK

    A. D. Buckingham

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  1. A. D. Buckingham
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Editor information

Editors and Affiliations

  1. Departamento de Química, Universidade de Coimbra, Coimbra, Portugal

    José J. C. Teixeira-Dias

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© 1992 Springer Science+Business Media Dordrecht

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Buckingham, A.D. (1992). Basic Theory of Intermolecular Forces. In: Teixeira-Dias, J.J.C. (eds) Molecular Liquids: New Perspectives in Physics and Chemistry. NATO ASI Series, vol 379. Springer, Dordrecht. https://doi.org/10.1007/978-94-011-2832-2_6

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  • DOI: https://doi.org/10.1007/978-94-011-2832-2_6

  • Publisher Name: Springer, Dordrecht

  • Print ISBN: 978-94-010-5258-0

  • Online ISBN: 978-94-011-2832-2

  • eBook Packages: Springer Book Archive

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