Letter | Published:

Intermolecular Potential Energy Functions for Simple Molecules

Nature volume 204, page 678 (14 November 1964) | Download Citation

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Abstract

THE development of an intermolecular potential energy function for simple molecules based solely on an investigation of properties arising from two-body interactions1 may prove more valuable than the alternative approach which considers also the properties of solids2. The latter approach involves the assumption of the pair-wise additivity of potential energy, the validity of which must be regarded as unproven. Unfortunately, the second virial coefficient, which is the most convenient two-body property to analyse, is not capable of defining a unique potential energy function3. However, recent low-temperature data provide a valuable test of the adequacy of potential energy functions and illustrate clearly the failure of many widely-used potentials4. Although some evidence points to a more complex form of the potential function, it seems appropriate to examine first simple two-term functions of the (n−6) type, which may be written: when rm is the separation of the molecular centres at the potential minimum. The collision diameter σ is related to rm by:

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Author information

Affiliations

  1. Physical Chemistry Laboratory, University of Oxford.

    • J. H. DYMOND
    • , M. RIGBY
    •  & E. B. SMITH

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DOI

https://doi.org/10.1038/204678a0

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