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

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 O(N4⁡log(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.