One-electron properties of several small molecules calculated using the local density approximation within density functional theory

Patrick Duffy, Delano P. Chong, Michel Dupuis

Research output: Contribution to journalArticle

29 Citations (Scopus)

Abstract

Density functional theory (DFT) is a field enjoying a tremendous recent surge in popularity among theoretical and practical chemists alike because of its ability to more easily handle larger molecular systems than conventional ab initio methods. Until recently, however, assessment of the quality of the properties predicted (and therefore the charge density) from DFT had been limited mainly to dipole moments and their nuclear coordinate and electric field derivatives. This paper presents the calculated results for some of the one-electron properties of the eight small molecules (NH3, PH 3, H2O, H2S, HF, HCl, CO, and N2). The properties chosen weight different regions of the charge density, from either very close in or at the nucleus (e.g., δ, the electron density at the nucleus) to regions farther out from the nucleus (e.g., the diamagnetic susceptibility 〈r2〉). It is found that properties which depend on an accurate knowledge of the electron density near to the nucleus are predicted poorly by the local density approximation (LDA), while others more dependent on the charge density farther out from the nucleus are predicted much more accurately, possibly due to cancellation of errors. Use of the LDA is therefore not recommended for "tight" properties; use of a functional employing gradient corrections would be more suitable for this purpose.

Original languageEnglish
Pages (from-to)3312-3321
Number of pages10
JournalJournal of Chemical Physics
Volume102
Issue number8
Publication statusPublished - 1995

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Local density approximation
Charge density
Density functional theory
density functional theory
Molecules
nuclei
Carrier concentration
Electrons
approximation
molecules
electrons
Dipole moment
Carbon Monoxide
Electric fields
Derivatives
cancellation
dipole moments
magnetic permeability
gradients
electric fields

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

One-electron properties of several small molecules calculated using the local density approximation within density functional theory. / Duffy, Patrick; Chong, Delano P.; Dupuis, Michel.

In: Journal of Chemical Physics, Vol. 102, No. 8, 1995, p. 3312-3321.

Research output: Contribution to journalArticle

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