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The use of systematic sequences of wave functions for estimating the complete basis set, full configuration interaction limit in water

1993; American Institute of Physics; Volume: 98; Issue: 9 Linguagem: Inglês

10.1063/1.464749

1520-9032

David Feller,

Photochemistry and Electron Transfer Studies

An assortment of 1- and 2-electron water properties were extracted from a systematic sequence of wave functions. The regularity inherent in this sequence permitted simple exponential fits of the resulting energies and, in many cases, the properties. To the extent the exponential fit accurately reflects the asymptotic convergence of a specific property, it provides an estimate of the complete basis set, full configuration interaction (CI) limiting value at a reduced computational expense. As a consequence of the vast reduction in the number of configurations that must be treated variationally, the proposed scheme may make possible improved estimates of the complete basis set, full CI limit beyond what could be obtained from explicit computations. In order to judge the accuracy of the procedure, we have carried out the highest level ab initio calculations to date on water, recovering in excess of 96% of the estimated valence correlation energy.