Linearity condition for orbital energies in density functional theory: Construction of orbital-specific hybrid functional

Yutaka Imamura, Rie Kobayashi, Hiromi Nakai

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This study proposes a novel approach to construct the orbital-specific (OS) hybrid exchange-correlation functional by imposing the linearity condition: 2E/fi|0fi1=i/fi|0fi1=0, where E, i, and fi represent the total energy, orbital energy, and occupation number of the ith orbital. The OS hybrid exchange-correlation functional, of which the OS Hartree-Fock exchange (HFx) portion is determined by the linearity condition, reasonably reproduces the ionization potentials not only from valence orbitals but also from core ones in a sense of Koopmans' theorem. The obtained short-range HFx portions are consistent with the parameters empirically determined in core-valence-Rydberg-Becke-3-parameter-Lee- Yang-Parr hybrid functional Nakata, J. Chem. Phys., 124, 094105 (2006); ibid, 125, 064109 (2006)10.1063/1.2227379

Original languageEnglish
Article number124113
JournalJournal of Chemical Physics
Issue number12
Publication statusPublished - 2011 Mar 28


ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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