Abstract
The realism of a computer simulation is usually limited by the accuracy of the fundamental scientific input into the calculation: the model intermolecular potential. We examine the problems in establishing accurate model potentials, by considering the physical origins of intermolecular forces, highlighting the approximations which are usually made in the potentials used in simulations, and discussing the problems in quantifying intermolecular potentials by ab initio methods and by fitting to experimental data. This emphasises the importance of choosing a realistic functional form for the potential. The isotropic atom-atom model potential, which is usually used for modelling polyatomic molecules, is contrasted with the recently developed anisotropic site-site approach to designing model potentials. The electrostatic interaction can be represented very accurately within the anisotropic site-site formalism, by the use of an ab initio based distributed multipole model. We show how empirical anisotropic site-site potentials have been used to great effect in a Molecular Dynamics simulation of liquid chlorine and Monte Carlo simulations of three condensed phases of benzene. Thus we can expect that the use of such model potentials will lead to more realistic simulations in the future.
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Price, S.L. (1990). Towards Realistic Model Intermolecular Potentials. In: Catlow, C.R.A., Parker, S.C., Allen, M.P. (eds) Computer Modelling of Fluids Polymers and Solids. NATO ASI Series, vol 293. Springer, Dordrecht. https://doi.org/10.1007/978-94-009-2484-0_2
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DOI: https://doi.org/10.1007/978-94-009-2484-0_2
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