MEASURES OF THE SMALL CORE-VALENCE AND CORE-CORE CORRELATION ENERGY ERRORS IN THE OPTIMIZED VALENCE CONFIGURATIONS (OVC) METHOD OF DAS AND WAHL

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1984

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Ohio State University

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The OVC version [1] of the multiconfiguration self consistent field approach in ab initio quantum-mechanical computations of small molecules has met with a reasonable measure of success. Even when pushed to the hilt (as we have attempted to do for low-lying states of $Li_{2}$, for example [1]), the OVC scheme gave potential curves which were slightly misshapen ($\omega_{e}$ and $B_{e}$ too small, for example). Effective core potential computations [2] and very refined spectroscopic observations [3,4] help to understand and quantify those small defects.

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$^{1}$G. Das and A.C. Wahl, J. Chem. Phys. 47, 2934 (1967). $^{2}$D.D. Konowalow and M.L. Olson, J. Chem. Phys. 71, 450 (1979). $^{3}$D.D. Konowalow and J.L. Fish, Chem. Phys. (in press). $^{4}$K.K. Verma, M.E. Koch and W.C. Stwalley, J. Chem. Phys. 78, 3614 (1983). $^{5}$J. Verges, R. Bacis, B. Barakat, P. Carrot, S. Churassy and P. Crozet, Chem. Phys. Lett. 98, 203 (1983).
Author Institution: Department of Chemistry, State University of New York at Binghamton

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