To assess the performance of multi-configuration methods using exact exchange Kohn-Sham (KS) orbitals, we implemented configuration interaction singles and doubles (CISD) in a real-space numerical grid code. We obtained KS orbitals with the exchange-only optimized effective potential under the Krieger-Li-Iafrate (KLI) approximation. Thanks to the distinctive features of KLI orbitals against Hartree-Fock (HF), such as bound virtual orbitals with compact shapes and orbital energy gaps similar to excitation energies; KLI-CISD for small molecules shows much faster convergence as a function of simulation box size and active space (i.e., the number of virtual orbitals) than HF-CISD. The former also gives more accurate excitation energies with a few dominant configurations than the latter, even with many more configurations. The systematic control of basis set errors is straightforward in grid bases. Therefore, grid-based multi-configuration methods using exact exchange KS orbitals provide a promising new way to make accurate electronic structure calculations.
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14 December 2016
Research Article|
December 15 2016
Outstanding performance of configuration interaction singles and doubles using exact exchange Kohn-Sham orbitals in real-space numerical grid method
Jaechang Lim;
Jaechang Lim
Department of Chemistry,
KAIST
, 291 Daehak-ro, Yuseong-gu, Daejeon 34141, South Korea
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Sunghwan Choi;
Sunghwan Choi
Department of Chemistry,
KAIST
, 291 Daehak-ro, Yuseong-gu, Daejeon 34141, South Korea
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Jaewook Kim;
Jaewook Kim
Department of Chemistry,
KAIST
, 291 Daehak-ro, Yuseong-gu, Daejeon 34141, South Korea
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Woo Youn Kim
Woo Youn Kim
a)
Department of Chemistry,
KAIST
, 291 Daehak-ro, Yuseong-gu, Daejeon 34141, South Korea
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a)
Author to whom correspondence should be addressed. Electronic mail: [email protected]
J. Chem. Phys. 145, 224309 (2016)
Article history
Received:
July 27 2016
Accepted:
November 23 2016
Citation
Jaechang Lim, Sunghwan Choi, Jaewook Kim, Woo Youn Kim; Outstanding performance of configuration interaction singles and doubles using exact exchange Kohn-Sham orbitals in real-space numerical grid method. J. Chem. Phys. 14 December 2016; 145 (22): 224309. https://doi.org/10.1063/1.4971786
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