Cubic-scaling algorithm and self-consistent field for the random-phase approximation with second-order screened exchange

preprint2014arXivOpen access

Abstract

The random-phase approximation with second-order screened exchange (RPA+SOSEX) is a model of electron correlation energy with two caveats: its accuracy depends on an arbitrary choice of mean field, and it scales as O(n5)\mathcal{O}(n^5) operations and O(n3)\mathcal{O}(n^3) memory for nn electrons. We derive a new algorithm that reduces its scaling to O(n3)\mathcal{O}(n^3) operations and O(n2)\mathcal{O}(n^2) memory using controlled approximations and a new self-consistent field that approximates Brueckner coupled-cluster doubles (BCCD) theory with RPA+SOSEX, referred to as Brueckner RPA (BRPA) theory. The algorithm comparably reduces the scaling of second-order Mø\mathrm{ø}ller-Plesset (MP2) perturbation theory with smaller cost prefactors than RPA+SOSEX. Within a semiempirical model, we study H2_2 dissociation to test accuracy and Hn_n rings to verify scaling.

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