Can We Avoid the Intruder-State Problems in the State-Universal Coupled-Cluster Approaches While Preserving Size Extensivity?

Abstract

Following the analysis of principal bottlenecks in the extension of the single-reference (SR) coupled-cluster (CC) methodology to the multireference (MR) case, we review and discuss some recent developments that facilitate the use of general model spaces (GMSs) within the state universal (SU) or Hilbert space MR CC formalism. The use of a GMS improves our ability to avoid the intruder state problems. This feature is further enhanced by generalizing the idea of the externally corrected (ec) SR CC formalism to the MR situations. In this latter approach we employ the cluster analysis to extract the most important higher-than-pair cluster amplitudes from a suitable set of known wave functions. Similarly to the SR case, the most convenient external source is represented by wave functions that are obtained via a modest size MR configuration interaction (CI), which employs an N-dimensional reference space. The resulting higher-than-pair cluster amplitudes are subsequently used in the SU CCSD method that is based on an M-dimensional GMS avoiding intruders. We discuss general aspects of these developments from various viewpoints and provide selective illustrations of the key concepts and ideas.