TY - JOUR
T1 - Linearity condition for orbital energies in density functional theory
T2 - Construction of orbital-specific hybrid functional
AU - Imamura, Yutaka
AU - Kobayashi, Rie
AU - Nakai, Hiromi
N1 - Funding Information:
Some of the present calculations were performed at the Research Center for Computational Science (RCCS), Okazaki Research Facilities, National Institutes of Natural Sciences (NINS). This study was supported in part by Grants-in-Aid for Challenging Exploratory Research “KAKENHI 22655008” from the Ministry of Education, Culture, Sports, Science and Technology (MEXT), Japan; by the Nanoscience Program in the Next Generation Super Computing Project of the MEXT; by the Global Center Of Excellence (COE) “Practical Chemical Wisdom” from the MEXT; by a Waseda University Grant for Special Research Projects (2010B-156); and by a project research grant for “Practical in-silico chemistry for material design” from the Research Institute for Science and Engineering (RISE), Waseda University.
PY - 2011/3/28
Y1 - 2011/3/28
N2 - 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
AB - 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
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U2 - 10.1063/1.3569030
DO - 10.1063/1.3569030
M3 - Article
C2 - 21456651
AN - SCOPUS:79953326966
SN - 0021-9606
VL - 134
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
IS - 12
M1 - 124113
ER -