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How Much Dispersion Energy Is Included in the Multiconfigurational Interaction Energy?

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cris.lastimport.scopus2024-02-12T20:52:11Z
dc.abstract.enWe demonstrate how to quantify the amount of dispersion interaction recovered by supermolecular calculations with the multiconfigurational self-consistent field (MCSCF) wave functions. For this purpose, we present a rigorous derivation which connects the portion of dispersion interaction captured by the assumed wave function modelthe residual dispersion interaction with the size of the active space. Based on the obtained expression for the residual dispersion contribution, we propose a dispersion correction for the MCSCF that avoids correlation double counting. Numerical demonstration for model fourelectron dimers in both ground and excited states described with the complete active space self-consistent field (CASSCF) reference serves as a proof-of-concept for the method. Accurate results, largely independent of the size of the active space, are obtained. For many-electron systems, routine CASSCF interaction energy calculations recover a tiny fraction of the full second-order dispersion energy. We found that the residual dispersion is non-negligible only for purely dispersion-bound complexes.
dc.affiliationUniwersytet Warszawski
dc.contributor.authorHapka, Michał
dc.contributor.authorPernal, Katarzyna
dc.contributor.authorKrzemińska-Kowalska, Agnieszka
dc.date.accessioned2024-01-25T03:30:09Z
dc.date.available2024-01-25T03:30:09Z
dc.date.copyright2020-09-01
dc.date.issued2020
dc.description.accesstimeAT_PUBLICATION
dc.description.financePublikacja bezkosztowa
dc.description.number10
dc.description.versionFINAL_PUBLISHED
dc.description.volume16
dc.identifier.doi10.1021/ACS.JCTC.0C00681
dc.identifier.issn1549-9618
dc.identifier.urihttps://repozytorium.uw.edu.pl//handle/item/108670
dc.identifier.weblinkhttp://pubs.acs.org/doi/pdf/10.1021/acs.jctc.0c00681
dc.languageeng
dc.pbn.affiliationchemical sciences
dc.relation.ispartofJournal of Chemical Theory and Computation
dc.relation.pages6280-6293
dc.rightsCC-BY
dc.sciencecloudnosend
dc.titleHow Much Dispersion Energy Is Included in the Multiconfigurational Interaction Energy?
dc.typeJournalArticle
dspace.entity.typePublication