Static polarizabilities within the generalized Kohn–Sham semicanonical projected random phase approximation (GKS-spRPA)

Author:

Balasubramani Sree Ganesh12ORCID,Voora Vamsee K.2ORCID,Furche Filipp2ORCID

Affiliation:

1. Department of Chemistry and Biochemistry, University of Arizona, 1306 East University Blvd., Tucson, Arizona 85721, USA

2. Department of Chemistry, University of California, Irvine, 1102 Natural Sciences II, Irvine, California 92697-2025, USA

Abstract

An 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 [Formula: see text] scaling of operation count and [Formula: see text] 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 (Na n 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.

Funder

National Science Foundation

Publisher

AIP Publishing

Subject

Physical and Theoretical Chemistry,General Physics and Astronomy

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