A COMPARISON OF EMPIRICAL AND AB INITIO POTENTIAL ENERGY SURFACES FOR $Ar-H_{2}$ Carey Bissonnette.

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1993

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Ohio State University

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Abstract

The most accurate published intermolecular potential for $Ar-H_{2}$ was obtained more than five years ago by Le Roy and $Hutson^{1}$ from a fit to infrared and microwave spectroscopic data and differential cross section measurements. Potentials energy surfaces for $Ar-H_{2}$ obtained from ab initio calculations have been proposed $recently,^{2-3}$ but they have not been tested directly against those data. Although $Ar-H_{2}$ is one of the simplest Van der Waals complexes, it is one of the first systems for which fully dimensional ab initio potentials are available, so this provides a unique opportunity to assess quantitatively the accuracy of intermolecular potentials which are obtained ab initio. We have used these theoretical potential energy surfaces for $Ar-H_{2}$ to calculate infrared and microwave transition frequencies for comparison with experiment. The results of these calculations will be presented and discussed.

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$^{1}$ R.J. Le Roy and J.M. Hutson, J. Chem. Phys. 86, 837 (1987). $^{2}$ R.J. Wheatley and W.J. Meath, unpublished work (1992). 3 H.L. Williams, K. Szalewicz, B. Jeziorski, K. Moszynski and S. Rybak, J. Chem. Phys. 98, 1279 (1993).
Author Institution: Guelph-Waterloo Centre for Graduate Work in Chemistry, University of Waterloo.; Department of Chemistry, University of Western Ontario

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