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Dynamically weighted multireference perturbation theory: Combining the advantages of multi-state and state-averaged methods
Emory Univ, Dept Chem, Atlanta, GA 30322 USA;Emory Univ, Cherry Emerson Ctr Sci Computat, Atlanta, GA 30322 USA.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Theoretical Chemistry. (Uppsala Center for Computational Chemistry)ORCID iD: 0000-0001-7567-8295
Emory Univ, Dept Chem, Atlanta, GA 30322 USA;Emory Univ, Cherry Emerson Ctr Sci Computat, Atlanta, GA 30322 USA.
2019 (English)In: Journal of Chemical Physics, ISSN 0021-9606, E-ISSN 1089-7690, Vol. 150, no 14, article id 144107Article in journal (Refereed) Published
Abstract [en]

We introduce two new approaches to compute near-degenerate electronic states based on the driven similarity renormalization group (DSRG) framework. The first approach is a unitary multi-state formalism based on the DSRG (MS-DSRG), whereby an effective Hamiltonian is built from a set of state-specific solutions. The second approach employs a dynamic weighting parameter to smoothly interpolate between the multi-state and the state-averaged DSRG schemes. The resulting dynamically weighted DSRG (DW-DSRG) theory incorporates the most desirable features of both multi-state approaches (ability to accurately treat many states) and state-averaged methods (correct description of avoided crossings and conical intersections). We formulate second-order perturbation theories (PT2) based on the MS-and DW-DSRG and study the potential energy curves of LiF, the conical intersection of the two lowest singlet states of NH3, and several low-lying excited states of benzene, naphthalene, and anthracene. The DW-DSRG-PT2 predicts the correct avoided crossing of LiF and avoids artifacts produced by the corresponding state-specific and multi-state theories. Excitation energies of the acenes computed with the DW-DSRG-PT2 are found to be more accurate than the corresponding state-averaged values, showing a small dependence on the number of states computed.

Place, publisher, year, edition, pages
2019. Vol. 150, no 14, article id 144107
National Category
Theoretical Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-382850DOI: 10.1063/1.5088120ISI: 000464451300010PubMedID: 30981256OAI: oai:DiVA.org:uu-382850DiVA, id: diva2:1317347
Funder
Swedish Research Council, 2016-03398Wenner-Gren FoundationsAvailable from: 2019-05-22 Created: 2019-05-22 Last updated: 2019-05-22Bibliographically approved

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