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The size-extensitivity of correlation energy estimators based on effective characteristic polynomials

Herbert H. H.Homeier
Institut für Physikalische und Theoretische Chemie
Universität Regensburg
D-93040 Regensburg, Germany

Abstract:

Estimators tex2html_wrap_inline331 for the correlation energy can be computed as roots of effective characteristic polynomials of degree n. The coefficients of these polynomials are derived from the terms of the perturbation series of the energy. From a fourth-order Møller-Plesset (MP4) calculation one can calculate with negligible effort a size-extensive estimator tex2html_wrap_inline335 that is in many cases much closer to the full CI correlation energy of the ground state than the MP4 value. [H.H.H. Homeier, J. Mol. Struct. (Theochem) 366, 161 (1996)] Here, we prove that the estimators tex2html_wrap_inline331 for n>2 are size-extensive if they are calculated from the MP series.

Keywords: Convergence acceleration -- ab initio method -- Extrapolation -- Many-body perturbation theory -- Møller-Plesset series




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Next: Introduction Up: The size-extensitivity of correlation

Herbert H. H. Homeier (herbert.homeier@na-net.ornl.gov)