ISSN:
0020-7608
Keywords:
Computational Chemistry and Molecular Modeling
;
Atomic, Molecular and Optical Physics
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The goodness of the local fit of an approximate wave-function, \documentclass{article}\pagestyle{empty}\begin{document}$ \tilde \psi $\end{document}, to the exact function, ψ0, is \documentclass{article}\pagestyle{empty}\begin{document}$ |\tilde \psi - \psi _0 | $\end{document}. From this quantity the global accuracy of \documentclass{article}\pagestyle{empty}\begin{document}$ \tilde \psi $\end{document} is defined and a “working supposition” is presented, which quantitatively relates the global accuracy to the accuracy of expectation values. Two criteria based on the accuracy of the reduced local energy and the density respectively, are presented as alternatives to \documentclass{article}\pagestyle{empty}\begin{document}$ |\tilde \psi - \psi _0 | $\end{document}. The relative global accuracies of eight wave-functions for H2 are determined using the two criteria. The ‘working supposition’ is applied and predictions are made concerning the relative accuracies of the expectation values of the following operators: z2, r2, x2 + y2, 3z2 -; r2, ξ, rA-1, r12-1, and EL (the reduced local energy). The success rate is high (〉90%) except for those operators which are sensitive to interelectron coordinates or derivatives of the wave-function.
Additional Material:
4 Tab.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/qua.560110106
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