Toward a Stochastic Complete Active Space Second-Order Perturbation Theory.

ABSTRACT

In this work, an internally contracted stochastic complete active space second-order perturbation theory, stochastic-CASPT2, is reported. The method relies on stochastically sampled reduced density matrices (RDMs) up to rank four and contractions thereof with the generalized Fock matrix. A new protocol for calculating higher-order RDMs in full configuration interaction quantum Monte Carlo (FCIQMC) has been designed based on (1) restricting sampling of the corresponding excitations to a deterministic subspace, (2) averaging the RDMs from independent dynamics and (3) projecting them onto the closest positive semi-definite matrix. Our protocol avoids previously encountered numerical conditioning problems in the orthogonalization of the perturber overlap matrix stemming from numerical noise. The chromium dimer CASSCF(12,12)/CASPT2 binding curve is computed as a proof of concept.