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Title: Validity of virial theorem in all-electron mixed basis density functional, Hartree–Fock, and GW calculations

In this paper, we calculate kinetic and potential energy contributions to the electronic ground-state total energy of several isolated atoms (He, Be, Ne, Mg, Ar, and Ca) by using the local density approximation (LDA) in density functional theory, the Hartree–Fock approximation (HFA), and the self-consistent GW approximation (GWA). To this end, we have implemented self-consistent HFA and GWA routines in our all-electron mixed basis code, TOMBO. We confirm that virial theorem is fairly well satisfied in all of these approximations, although the resulting eigenvalue of the highest occupied molecular orbital level, i.e., the negative of the ionization potential, is in excellent agreement only in the case of the GWA. We find that the wave function of the lowest unoccupied molecular orbital level of noble gas atoms is a resonating virtual bound state, and that of the GWA spreads wider than that of the LDA and thinner than that of the HFA.
Authors:
 [1] ;  [2] ; ;  [1]
  1. Department of Physics, Yokohama National University, 79-5 Tokiwadai, Hodogaya-ku, Yokohama 240-8501 (Japan)
  2. (Japan)
Publication Date:
OSTI Identifier:
22419823
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 141; Journal Issue: 8; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ATOMS; BOUND STATE; DENSITY; DENSITY FUNCTIONAL METHOD; EIGENVALUES; ELECTRONS; GROUND STATES; HARTREE-FOCK METHOD; MOLECULAR ORBITAL METHOD; POTENTIAL ENERGY