Locally range-separated hybrid (LRSH) functionals feature a real-space-dependent range separation function (RSF) instead of a system-independent range-separation parameter, which thus enables a more flexible admixture of exact exchange than conventional range-separated hybrid functionals. In particular, the development of suitable RSF models and exploring the capabilities of the LRSH approach, in general, are tasks that require further investigations and will be addressed in this work. We propose a non-empirical scheme based on a detailed scaling analysis with respect to a uniform coordinate scaling and on a short-range expansion of the range-separated exchange energy density to derive new RSF models from a gradient expansion of the exchange energy density. After optimizing a small set of empirical parameters introduced to enhance their flexibility, the resulting second- and fourth-order RSFs are evaluated with respect to atomic exchange energies, atomization energies, and transition barrier heights.
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7 June 2021
Research Article|
June 01 2021
Assessing locally range-separated hybrid functionals from a gradient expansion of the exchange energy density
Toni M. Maier
;
Toni M. Maier
a)
1
Technische Universität Berlin, Institut für Chemie, Theoretische Chemie/Quantenchemie
, Sekr. C7, Straße des 17. Juni 135, D-10623 Berlin, Germany
a)Author to whom correspondence should be addressed: t.maier@campus.tu-berlin.de
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Yasuhiro Ikabata
;
Yasuhiro Ikabata
2
Waseda Research Institute for Science and Engineering, Waseda University
, 3-4-1 Okubo, Shinjuku-ku, Tokyo 169-8555, Japan
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Hiromi Nakai
Hiromi Nakai
b)
2
Waseda Research Institute for Science and Engineering, Waseda University
, 3-4-1 Okubo, Shinjuku-ku, Tokyo 169-8555, Japan
3
Department of Chemistry and Biochemistry, School of Advanced Science and Engineering, Waseda University
, 3-4-1 Okubo, Shinjuku-ku, Tokyo 169-8555, Japan
4
Elements Strategy Initiative for Catalysts and Batteries (ESICB), Kyoto University
, Katsura, Kyoto 615-8520, Japan
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a)Author to whom correspondence should be addressed: t.maier@campus.tu-berlin.de
b)
Electronic mail: nakai@waseda.jp
J. Chem. Phys. 154, 214101 (2021)
Article history
Received:
February 15 2021
Accepted:
May 09 2021
Citation
Toni M. Maier, Yasuhiro Ikabata, Hiromi Nakai; Assessing locally range-separated hybrid functionals from a gradient expansion of the exchange energy density. J. Chem. Phys. 7 June 2021; 154 (21): 214101. https://doi.org/10.1063/5.0047628
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