We present an implementation of time-dependent linear-response equations for strongly orthogonal geminal wave function models: the time-dependent generalized valence bond (TD-GVB) perfect-pairing theory and the antisymmetrized product of strongly orthogonal geminals. The geminal wave functions are optimized using a restricted-step second-order algorithm suitable for handling many geminals, and the linear-response equations are solved in an efficient way using a direct iterative approach. The wave function optimization algorithm features an original scheme to create initial orbitals for the geminal functions in a black-box fashion. The implementation is employed to examine the accuracy of the geminal linear response for singlet excitation energies of small and medium-sized molecules. In systems dominated by dynamic correlation, geminal models constitute only a minor improvement with respect to time-dependent Hartree–Fock. Compared to the linear-response complete active space self-consistent field, TD-GVB either misses or gives large errors for states dominated by double excitations.
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7 May 2022
Research Article|
May 02 2022
An efficient implementation of time-dependent linear-response theory for strongly orthogonal geminal wave function models
Michał Hapka
;
Michał Hapka
a)
1
Faculty of Chemistry, University of Warsaw
, ul. L. Pasteura 1, 02-093 Warsaw, Poland
2
Department of Physics, Chemistry and Pharmacy, University of Southern Denmark
, Campusvej 55, DK-5230 Odense M, Denmark
a)Author to whom correspondence should be addressed: michal.hapka@uw.edu.pl
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Katarzyna Pernal
;
Katarzyna Pernal
3
Institute of Physics, Lodz University of Technology
, ul. Wolczanska 217/221, 93-005 Lodz, Poland
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Hans Jørgen Aa. Jensen
Hans Jørgen Aa. Jensen
b)
2
Department of Physics, Chemistry and Pharmacy, University of Southern Denmark
, Campusvej 55, DK-5230 Odense M, Denmark
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a)Author to whom correspondence should be addressed: michal.hapka@uw.edu.pl
b)
Electronic mail: hjj@sdu.dk
J. Chem. Phys. 156, 174102 (2022)
Article history
Received:
December 13 2021
Accepted:
April 14 2022
Citation
Michał Hapka, Katarzyna Pernal, Hans Jørgen Aa. Jensen; An efficient implementation of time-dependent linear-response theory for strongly orthogonal geminal wave function models. J. Chem. Phys. 7 May 2022; 156 (17): 174102. https://doi.org/10.1063/5.0082155
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