TY - JOUR
T1 - Time-dependent density functional theory calculations for core-excited states
T2 - Assessment of standard exchange-correlation functionals and development of a novel hybrid functional
AU - Nakata, Ayako
AU - Imamura, Yutaka
AU - Otsuka, Takao
AU - Nakai, Hiromi
N1 - Funding Information:
The calculations were performed in part at the Research Center for Computational Science (RCCS) of the Okazaki National Research Institutes. This study was partially supported by a Grant-in-Aid for Exploratory Research, KAKENHI 16655010, from the Japanese Ministry of Education, Culture, Sports, Science and Technology (MEXT), Japan, a NAREGI Nano-Science Project of MEXT, the 21st Century Center Of Excellence (21COE) “Practical Nano-Chemistry” from MEXT, and the “Development of high-performance computational environment for quantum chemical calculation and its assessment” from the Advanced Research Institute for Science and Engineering (RISE), Waseda University. Three of the authors (A. N., Y. I., and T. O.) are indebted for the JSPS Research Fellowship for Young Scientists.
PY - 2006
Y1 - 2006
N2 - A new hybrid functional for accurate descriptions of core and valence excitations, the core-valence Becke's three-parameter exchange (B3)+Lee-Yang-Paar (LYP) correlation functional (CV-B3LYP), is proposed. The construction of the new hybrid functional is based on the assessment that B3LYP performs well for properties concerning valence electrons and Becke's half-and-half exchange+LYP functional (BHHLYP), which includes 50% portion of Hartree-Fock exchange, performs well for core excitations. By using the appropriate portions of Hartree-Fock exchange for core and valence regions separately, CV-B3LYP overcomes the disadvantages of BHHLYP and B3LYP, which give inferior descriptions of valence and core excitations, respectively. Density functional theory (DFT) calculations with the CV-B3LYP functional reproduce core- and valence-orbital energies close to those of BHHLYP and B3LYP, respectively. Time-dependent DFT calculations with the CV-B3LYP functional yield both core- and valence-excitation energies with reasonable accuracy.
AB - A new hybrid functional for accurate descriptions of core and valence excitations, the core-valence Becke's three-parameter exchange (B3)+Lee-Yang-Paar (LYP) correlation functional (CV-B3LYP), is proposed. The construction of the new hybrid functional is based on the assessment that B3LYP performs well for properties concerning valence electrons and Becke's half-and-half exchange+LYP functional (BHHLYP), which includes 50% portion of Hartree-Fock exchange, performs well for core excitations. By using the appropriate portions of Hartree-Fock exchange for core and valence regions separately, CV-B3LYP overcomes the disadvantages of BHHLYP and B3LYP, which give inferior descriptions of valence and core excitations, respectively. Density functional theory (DFT) calculations with the CV-B3LYP functional reproduce core- and valence-orbital energies close to those of BHHLYP and B3LYP, respectively. Time-dependent DFT calculations with the CV-B3LYP functional yield both core- and valence-excitation energies with reasonable accuracy.
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U2 - 10.1063/1.2173987
DO - 10.1063/1.2173987
M3 - Article
AN - SCOPUS:34547237046
SN - 0021-9606
VL - 124
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
IS - 9
M1 - 094105
ER -