Multiple-resonance local wave functions for accurate excited states in quantum Monte Carlo

Habiburrahman Zulfikri, Claudio Amovilli, Claudia Filippi

Research output: Contribution to journalArticleAcademicpeer-review

7 Citations (Scopus)
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Abstract

We introduce a novel class of local multideterminant Jastrow–Slater wave functions for the efficient and accurate treatment of excited states in quantum Monte Carlo. The wave function is expanded as a linear combination of excitations built from multiple sets of localized orbitals that correspond to the bonding patterns of the different Lewis resonance structures of the molecule. We capitalize on the concept of orbital domains of local coupled-cluster methods, which is here applied to the active space to select the orbitals to correlate and construct the important transitions. The excitations are further grouped into classes, which are ordered in importance and can be systematically included in the Jastrow–Slater wave function to ensure a balanced description of all states of interest. We assess the performance of the proposed wave function in the calculation of vertical excitation energies and excited-state geometry optimization of retinal models whose π → π* state has a strong intramolecular charge-transfer character. We find that our multiresonance wave functions recover the reference values of the total energies of the ground and excited states with only a small number of excitations and that the same expansion can be flexibly used at very different geometries. Furthermore, significant computational saving can also be gained in the orbital optimization step by selectively mixing occupied and virtual orbitals based on spatial considerations without loss of accuracy on the excitation energy. Our multiresonance wave functions are therefore compact, accurate, and very promising for the calculation of multiple excited states of different character in large molecules.
Original languageEnglish
Pages (from-to)1157-1168
Number of pages12
JournalJournal of chemical theory and computation
Volume12
Issue number3
DOIs
Publication statusPublished - 2016

Keywords

  • METIS-319091
  • IR-103715

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