Hybrid exchange-correlation functional for core, valence, and Rydberg excitations: Core-valence-Rydberg B3LYP

Ayako Nakata; Yutaka Imamura; Hiromi Nakai

doi:10.1063/1.2227379

Hybrid exchange-correlation functional for core, valence, and Rydberg excitations: Core-valence-Rydberg B3LYP

Ayako Nakata, Yutaka Imamura, Hiromi Nakai^*

^*Corresponding author for this work

School of Advanced Science and Engineering

Research output: Contribution to journal › Article › peer-review

65 Citations (Scopus)

Abstract

The core-valence-Rydberg Becke's three-parameter exchange (B3)+Lee-Yang-Parr (LYP) correlation functional (CVR-B3LYP) is proposed as a means to improve descriptions of Rydberg excitations of core-valence B3LYP (CV-B3LYP). CV-B3LYP describes excitations from both core and occupied valence orbitals to unoccupied valence orbitals with high accuracy but fails to describe those to Rydberg orbitals. CVR-B3LYP, which adopts the appropriate portions of Hartree-Fock exchange for unoccupied valence and Rydberg regions separately, overcomes the disadvantage of CV-B3LYP. Numerical assessment confirms that time-dependent density functional theory calculations with CVR-B3LYP succeed in describing not only core excitations but also Rydberg excitations with reasonable accuracy.

Original language	English
Article number	064109
Journal	Journal of Chemical Physics
Volume	125
Issue number	6
DOIs	https://doi.org/10.1063/1.2227379
Publication status	Published - 2006

ASJC Scopus subject areas

Physics and Astronomy(all)
Physical and Theoretical Chemistry

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title = "Hybrid exchange-correlation functional for core, valence, and Rydberg excitations: Core-valence-Rydberg B3LYP",

abstract = "The core-valence-Rydberg Becke's three-parameter exchange (B3)+Lee-Yang-Parr (LYP) correlation functional (CVR-B3LYP) is proposed as a means to improve descriptions of Rydberg excitations of core-valence B3LYP (CV-B3LYP). CV-B3LYP describes excitations from both core and occupied valence orbitals to unoccupied valence orbitals with high accuracy but fails to describe those to Rydberg orbitals. CVR-B3LYP, which adopts the appropriate portions of Hartree-Fock exchange for unoccupied valence and Rydberg regions separately, overcomes the disadvantage of CV-B3LYP. Numerical assessment confirms that time-dependent density functional theory calculations with CVR-B3LYP succeed in describing not only core excitations but also Rydberg excitations with reasonable accuracy.",

author = "Ayako Nakata and Yutaka Imamura and Hiromi Nakai",

note = "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. Two of the authors (A.N. and Y.I.) are indebted for the JSPS Research Fellowship for Young Scientists.",

year = "2006",

doi = "10.1063/1.2227379",

language = "English",

volume = "125",

journal = "Journal of Chemical Physics",

issn = "0021-9606",

publisher = "American Institute of Physics Publising LLC",

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AU - Imamura, Yutaka

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. Two of the authors (A.N. and Y.I.) are indebted for the JSPS Research Fellowship for Young Scientists.

PY - 2006

Y1 - 2006

N2 - The core-valence-Rydberg Becke's three-parameter exchange (B3)+Lee-Yang-Parr (LYP) correlation functional (CVR-B3LYP) is proposed as a means to improve descriptions of Rydberg excitations of core-valence B3LYP (CV-B3LYP). CV-B3LYP describes excitations from both core and occupied valence orbitals to unoccupied valence orbitals with high accuracy but fails to describe those to Rydberg orbitals. CVR-B3LYP, which adopts the appropriate portions of Hartree-Fock exchange for unoccupied valence and Rydberg regions separately, overcomes the disadvantage of CV-B3LYP. Numerical assessment confirms that time-dependent density functional theory calculations with CVR-B3LYP succeed in describing not only core excitations but also Rydberg excitations with reasonable accuracy.

AB - The core-valence-Rydberg Becke's three-parameter exchange (B3)+Lee-Yang-Parr (LYP) correlation functional (CVR-B3LYP) is proposed as a means to improve descriptions of Rydberg excitations of core-valence B3LYP (CV-B3LYP). CV-B3LYP describes excitations from both core and occupied valence orbitals to unoccupied valence orbitals with high accuracy but fails to describe those to Rydberg orbitals. CVR-B3LYP, which adopts the appropriate portions of Hartree-Fock exchange for unoccupied valence and Rydberg regions separately, overcomes the disadvantage of CV-B3LYP. Numerical assessment confirms that time-dependent density functional theory calculations with CVR-B3LYP succeed in describing not only core excitations but also Rydberg excitations with reasonable accuracy.

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Hybrid exchange-correlation functional for core, valence, and Rydberg excitations: Core-valence-Rydberg B3LYP

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