Static polarizabilities within the generalized Kohn-Sham semicanonical projected random phase approximation (GKS-spRPA)
Final Published Version
AffiliationDepartment of Chemistry and Biochemistry, University of Arizona
MetadataShow full item record
PublisherAmerican Institute of Physics Inc.
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).
JournalJournal of Chemical Physics
RightsCopyright © 2022 Author(s). Published under an exclusive license by AIP Publishing.
Collection InformationThis 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 firstname.lastname@example.org.
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).
Note12 month embargo; published online: 26 October 2022
VersionFinal published version