Triple excitations in state-specific multireference coupled cluster theory: Application of Mk-MRCCSDT and Mk-MRCCSDT-n methods to model systems

Abstract

We report the first implementation with correct scaling of the Mukherjee multireference coupled cluster method with singles, doubles, and approximate iterative triples (Mk-MRCCSDT-n, n=1a,1b,2,3) as well as full triples (Mk-MRCCSDT). These methods were applied to the classic H4, P4, BeH(2), and H8 model systems to assess the ability of the Mk-MRCCSDT-n schemes to accurately account for triple excitations. In all model systems the inclusion of triples via the various Mk-MRCCSDT-n approaches greatly reduces the nonparallelism error (NPE) and the mean nonparallelism derivative diagnostics for the potential energy curves, recovering between 59% and 73% of the full triples effect on average. The most complete triples approximation, Mk-MRCCSDT-3, exhibits the best average performance, reducing the mean NPE to below 0.6 mE(h), compared to 1.4 mE(h) for Mk-MRCCSD. Both linear and quadratic truncations of the Mk-MRCC triples coupling terms are viable simplifications producing no significant errors. If the off-diagonal parts of the occupied-occupied and virtual-virtual blocks of the Fock matrices are ignored, the storage of the triples amplitudes is no longer required for the Mk-MRCCSDT-n methods introduced here. This proves to be an effective approximation that gives results almost indistinguishable from those derived from full consideration of the Fock matrices.