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Static polarizabilities within the generalized Kohn–Sham semicanonical projected random phase approximation (GKS-spRPA).
- Source :
-
Journal of Chemical Physics . 10/28/2022, Vol. 157 Issue 16, p1-12. 12p. - Publication Year :
- 2022
-
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 ( N 4 log (N)) scaling of operation count and O ( N 3 ) 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. [ABSTRACT FROM AUTHOR]
Details
- Language :
- English
- ISSN :
- 00219606
- Volume :
- 157
- Issue :
- 16
- Database :
- Academic Search Index
- Journal :
- Journal of Chemical Physics
- Publication Type :
- Academic Journal
- Accession number :
- 159958809
- Full Text :
- https://doi.org/10.1063/5.0103664