Reduced multireference CCSD method: An effective approach to quasidegenerate states

Abstract

Standard multireference (MR) coupled cluster (CC) approaches are based on the effective Hamiltonian formalism and generalized Bloch equation. Their implementation, relying on the valence universal or state universal cluster Ansatz, is very demanding and their practical exploitation is often plagued with intruder state and multiple solution problems. These problems are avoided in the so-called state selective or state specific (SS) MR approaches that concentrate on one state at a time. To preserve as much as possible the flexibility and generality offered by the general MR CC approaches, yet obtaining a reliable and manageable algorithm, we propose a novel SS strategy providing a size-extensive CC formalism, while exploiting the MR model space and the corresponding excited state manifold. This strategy involves three steps: (i) The construction of a variational configuration interaction (CI) wave function within the singly (S) and doubly (D) excited state manifold, (ii) the cluster analysis of this CI wave function providing the information about the higher than pair cluster amplitudes, and (iii) the exploitation of these amplitudes in the so-called externally corrected CCSD procedure. This approach is referred to as the reduced MR (RMR) SS CCSD method and is implemented at the ab initio level and applied to several model systems for which the exact full CI results are available. These include two four electron H4 systems (usually referred to as the H4 and S4 models), an eight electron H8 model and the singlet-triplet separation problem in CH2. It is shown that the RMR CCSD approach produces highly accurate results, is free from intruder state problems, is very general and effective and applicable to both closed and open shell systems.