Potential energy surfaces fur $OH(X\ ^{2}\Pi, A\ ^{2}\Sigma^{+})+$ rare gas open shell van der Waals complexes: How well can {ab initio} theory predict them?

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1994

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Ohio State University

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In the past few years many {ab initio} calculations have been performed to calculate potential energy surfaces for closed and open shell van der Waals complexes. The level of theory used ranges from SCF,CASSF, MRCI, to perturbation methods. To date, the most successful calculations for an open-shell system were made for $OH-Ar^{1}$. The calculated potential energy surface for the $A \ {^{2}}\Sigma^{+}$ state was in good agreement with the surface deducted from spectroscopic data However, the {ab initio} calculations appeared to underestimate the depth of the $X \ {^{2}}\Pi$ state potential surfaces. In the present work we report new CEPA potential surfaces for $OH(A, X)$-Rg complexes with Rg=He, Ne and Kr. For -Ne and -Kr, comparisons between the rovibronic energies predicted from the surfaces, and those measured experimentally, will be presented. For OH-He, predications of the binding energies and geometries will be reported.

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1) A.D. Eposti, H.J. Werner, J. Chem. Phys. 93(5), 3351 (1990)
Author Institution: Department of Chemistry, Emory University

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