The Bethe-Salpeter equation (BSE) based on GW quasiparticle levels is a successful approach for calculating the optical gaps and spectra of solids and also for predicting the neutral excitations of small molecules. We here present an all-electron implementation of the GW+BSE formalism for molecules, using numeric atom-centered orbital (NAO) basis sets. We present benchmarks for low-lying excitation energies for a set of small organic molecules, denoted in the literature as “Thiel’s set.” Literature reference data based on Gaussian-type orbitals are reproduced to about one millielectron-volt precision for the molecular benchmark set, when using the same GW quasiparticle energies and basis sets as the input to the BSE calculations. For valence correlation consistent NAO basis sets, as well as for standard NAO basis sets for ground state density-functional theory with extended augmentation functions, we demonstrate excellent convergence of the predicted low-lying excitations to the complete basis set limit. A simple and affordable augmented NAO basis set denoted “tier2+aug2” is recommended as a particularly efficient formulation for production calculations. We finally demonstrate that the same convergence properties also apply to linear-response time-dependent density functional theory within the NAO formalism.
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31 January 2020
Research Article|
January 24 2020
All-electron ab initio Bethe-Salpeter equation approach to neutral excitations in molecules with numeric atom-centered orbitals Available to Purchase
Chi Liu;
Chi Liu
1
Department of Chemistry, Duke University
, Durham, North Carolina 27708, USA
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Jan Kloppenburg;
Jan Kloppenburg
2
Institute of Condensed Matter and Nanoscience, Université Catholique de Louvain
, Louvain-la-Neuve 1348, Belgium
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Yi Yao
;
Yi Yao
3
Department of Chemistry, University of North Carolina
, Chapel Hill, North Carolina 27599, USA
4
Department of Mechanical Engineering and Materials Science, Duke University
, Durham, North Carolina 27708, USA
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Xinguo Ren
;
Xinguo Ren
5
CAS Key Laboratory of Quantum Information, University of Science and Technology of China
, Hefei, Anhui 230026, China
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Heiko Appel;
Heiko Appel
6
Max Planck Institute for the Structure and Dynamics of Matter, Center for Free Electron Laser Science
, 22761 Hamburg, Germany
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Yosuke Kanai
;
Yosuke Kanai
3
Department of Chemistry, University of North Carolina
, Chapel Hill, North Carolina 27599, USA
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Volker Blum
Volker Blum
a)
1
Department of Chemistry, Duke University
, Durham, North Carolina 27708, USA
4
Department of Mechanical Engineering and Materials Science, Duke University
, Durham, North Carolina 27708, USA
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Chi Liu
1
Jan Kloppenburg
2
Yi Yao
3,4
Xinguo Ren
5
Heiko Appel
6
Yosuke Kanai
3
Volker Blum
1,4,a)
1
Department of Chemistry, Duke University
, Durham, North Carolina 27708, USA
2
Institute of Condensed Matter and Nanoscience, Université Catholique de Louvain
, Louvain-la-Neuve 1348, Belgium
3
Department of Chemistry, University of North Carolina
, Chapel Hill, North Carolina 27599, USA
4
Department of Mechanical Engineering and Materials Science, Duke University
, Durham, North Carolina 27708, USA
5
CAS Key Laboratory of Quantum Information, University of Science and Technology of China
, Hefei, Anhui 230026, China
6
Max Planck Institute for the Structure and Dynamics of Matter, Center for Free Electron Laser Science
, 22761 Hamburg, Germany
a)
Electronic mail: [email protected]
J. Chem. Phys. 152, 044105 (2020)
Article history
Received:
August 04 2019
Accepted:
November 12 2019
Citation
Chi Liu, Jan Kloppenburg, Yi Yao, Xinguo Ren, Heiko Appel, Yosuke Kanai, Volker Blum; All-electron ab initio Bethe-Salpeter equation approach to neutral excitations in molecules with numeric atom-centered orbitals. J. Chem. Phys. 31 January 2020; 152 (4): 044105. https://doi.org/10.1063/1.5123290
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