First Ionization Energy as the Asymptotic Limit of the Average Local Electron Energy.

Autor:	El-Samman AM; Department of Chemistry, The University of Western Ontario, London, Ontario N6A 5B7, Canada., Ospadov E; Department of Chemistry, The University of Western Ontario, London, Ontario N6A 5B7, Canada., Staroverov VN; Department of Chemistry, The University of Western Ontario, London, Ontario N6A 5B7, Canada.
Jazyk:	angličtina
Zdroj:	Journal of chemical theory and computation [J Chem Theory Comput] 2020 Nov 10; Vol. 16 (11), pp. 6886-6893. Date of Electronic Publication: 2020 Oct 19.
DOI:	10.1021/acs.jctc.0c00806
Abstrakt:	The first vertical ionization energy of an atom or molecule is encoded in the rate of exponential decay of the exact natural orbitals. For natural orbitals represented in terms of Gaussian basis functions, this property does not hold even approximately. We show that it is nevertheless possible to deduce the first ionization energy from the long-range behavior of Gaussian-basis-set wave functions by evaluating the asymptotic limit of a quantity called the average local electron energy (ALEE), provided that the most diffuse functions of the basis set have a suitable shape and location. The ALEE method exposes subtle qualitative differences between seemingly analogous Gaussian basis sets and complements the extended Koopmans theorem by being robust in situations where the one-electron reduced density matrix is ill-conditioned.
Databáze:	MEDLINE
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