An efficient implementation of time-dependent linear-response theory for strongly orthogonal geminal wave function models

Michał Hapka, Katarzyna Pernal, Hans Jørgen Aa Jensen

Research output: Contribution to journalJournal articleResearchpeer-review

Abstract

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.

Original languageEnglish
Article number174102
JournalThe Journal of Chemical Physics
Volume156
Issue number17
ISSN0021-9606
DOIs
Publication statusPublished - 7. May 2022

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