Efficient calculation of beyond RPA correlation energies in the dielectric matrix formalism

Beuerle, Matthias; Graf, Daniel; Schurkus, Henry F. and Ochsenfeld, Christian (2018): Efficient calculation of beyond RPA correlation energies in the dielectric matrix formalism. In: Journal of Chemical Physics, Vol. 148, No. 20, 204104

Abstract

We present efficient methods to calculate beyond random phase approximation (RPA) correlation energies for molecular systems with up to 500 atoms. To reduce the computational cost, we employ the resolution-of-the-identity and a double-Laplace transform of the non-interacting polarization propagator in conjunction with an atomic orbital formalism. Further improvements are achieved using integral screening and the introduction of Cholesky decomposed densities. Our methods are applicable to the dielectric matrix formalism of RPA including second-order screened exchange (RPA-SOSEX), the RPAelectron-hole time-dependent Hartree-Fock (RPA-eh-TDHF) approximation, and RPArenormalized perturbation theory using an approximate exchange kernel (RPA-AXK). We give an application of our methodology by presenting RPA-SOSEX benchmark results for the L7 test set of large, dispersion dominated molecules, yielding a mean absolute error below1 kcal/mol. The presentwork enables calculating beyond RPA correlation energies for significantly larger molecules than possible to date, thereby extending the applicability of these methods to a wider range of chemical systems. Published by AIP Publishing.

• Item Type: Journal article
• Research Centers: Center for Integrated Protein Science Munich (CIPSM)
• Subjects: 500 Science > 540 Chemistry
• ISSN: 0021-9606
• Language: English