FCIQMC-Tailored Distinguishable Cluster Approach: Open-Shell Systems

Abstract

A recently proposed tailored approach based on the distinguishable cluster method and the stochastic FCI solver, FCIQMC [J. Chem. Theory Comput. 2020, 16, 5621], is extended to open-shell molecular systems. The method is employed to calculate spin gaps of various Fe(II) complexes, including a Fe(II) porphyrin model system. Both distinguishable cluster and fully relaxed CASSCF natural orbitals were used in this work as reference for the subsequent tailored distinguishable cluster calculations. The distinguishable cluster natural orbitals occupation numbers were also used as an aid to the selection of the active space. The effect of the active space sizes and of the explicit correlation correction (F12) onto the predicted spin gaps is investigated. The tailored distinguishable cluster with singles and doubles yields consistently more accurate results compared to the tailored coupled cluster with singles and doubles.