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dc.contributor.authorBalasubramani, S.G.
dc.contributor.authorVoora, V.K.
dc.contributor.authorFurche, F.
dc.date.accessioned2022-11-23T18:21:18Z
dc.date.available2022-11-23T18:21:18Z
dc.date.issued2022
dc.identifier.citationBalasubramani, S. G., Voora, V. K., & Furche, F. (2022). Static polarizabilities within the generalized Kohn-Sham semicanonical projected random phase approximation (GKS-spRPA). Journal of Chemical Physics, 157(16).
dc.identifier.issn0021-9606
dc.identifier.pmid36319432
dc.identifier.doi10.1063/5.0103664
dc.identifier.urihttp://hdl.handle.net/10150/666904
dc.description.abstractAn analytical implementation of static dipole polarizabilities within the generalized Kohn-Sham semicanonical projected random phase approximation (GKS-spRPA) method for spin-restricted closed-shell and spin-unrestricted open-shell references is presented. General second-order analytical derivatives of the GKS-spRPA energy functional are derived using a Lagrangian approach. By resolution-of-the-identity and complex frequency integration methods, an asymptotic O(N4â ilog(N)) scaling of operation count and O(N3) scaling of storage is realized, i.e., the computational requirements are comparable to those for GKS-spRPA ground state energies. GKS-spRPA polarizabilities are assessed for small molecules, conjugated long-chain hydrocarbons, metallocenes, and metal clusters, by comparison against Hartree-Fock (HF), semilocal density functional approximations (DFAs), second-order Møller-Plesset perturbation theory, range-separated hybrids, and experimental data. For conjugated polydiacetylene and polybutatriene oligomers, GKS-spRPA effectively addresses the "overpolarization"problem of semilocal DFAs and the somewhat erratic behavior of post-PBE RPA polarizabilities without empirical adjustments. The ensemble averaged GKS-spRPA polarizabilities of sodium clusters (Nan for n = 2, 3, ..., 10) exhibit a mean absolute deviation comparable to PBE with significantly fewer outliers than HF. In conclusion, analytical second-order derivatives of GKS-spRPA energies provide a computationally viable and consistent approach to molecular polarizabilities, including systems prohibitive for other methods due to their size and/or electronic structure. © 2022 Author(s).
dc.language.isoen
dc.publisherAmerican Institute of Physics Inc.
dc.rightsCopyright © 2022 Author(s). Published under an exclusive license by AIP Publishing.
dc.rights.urihttp://rightsstatements.org/vocab/InC/1.0/
dc.titleStatic polarizabilities within the generalized Kohn-Sham semicanonical projected random phase approximation (GKS-spRPA)
dc.typeArticle
dc.typetext
dc.contributor.departmentDepartment of Chemistry and Biochemistry, University of Arizona
dc.identifier.journalJournal of Chemical Physics
dc.description.note12 month embargo; published online: 26 October 2022
dc.description.collectioninformationThis item from the UA Faculty Publications collection is made available by the University of Arizona with support from the University of Arizona Libraries. If you have questions, please contact us at repository@u.library.arizona.edu.
dc.eprint.versionFinal published version
dc.source.journaltitleJournal of Chemical Physics


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