A universal explicit electron correlation correction applied to Mukherjee’s multi-reference perturbation theory

Abstract

We present a universally applicable explicit electron correlation (F12) correction and apply it to Mukherjee’s multi-reference perturbation theory (Mk-MRPT2). Two different F12 corrections are proposed: one is a universal F12 correction which is added to the conventional orbital correction, which is referred to as Mk-MRPT2+F12. In the second type of F12 correction the individual F12 contributions are added to each matrix element of the effective Hamiltonian. Subsequent diagonalization yields the Mk-MRPT2-F12 correction. Thereby, we achieve for both F12 corrections the accuracy of a quadruple-ζ basis set calculation when a triple-ζ basis set is employed and the F12 correction is added. Both F12 corrections reduce to MP2-F12/1A (fixed) in the single-reference limit.