Recoupling the singlet- and triplet-pairing channels in single-reference coupled cluster theory

Abstract

It is well known that single-reference coupled cluster theory truncated to low orders of excitations gives the right answer for the right reason when systems are dominated by dynamical or weak correlation. Static or strong correlation is more problematic, causing often catastrophic breakdown of restricted coupled cluster. This failure can be remedied, e.g., by allowing symmetry breaking in the reference or taking a multi-reference approach, but poses an interesting theoretical problem, especially since many groups have found that simplifying the T2 operator or the doubles amplitude equations gives better results. In singlet-paired coupled cluster, eliminating the triplet-pairing channel recovers reasonable qualitative behavior for strong correlation at the cost of a decreased description of dynamical correlation in weakly correlated situations. This behavior seems to hold for both closed- and open-shell systems. In this work, we explore the coupling of the singlet- and triplet-pairing channels of T2 and attempt to recouple them in order to recover dynamical correlation without reintroducing catastrophic failure due to strong correlation. In the weakly correlated regime, these pairing channels are only weakly coupled, and a simple recoupling gives good results. However, as strong correlation dominates, the coupling strength between the singlet- and triplet-pairing channels increases, making it difficult to perturbatively recouple the singlet- and triplet-pairing channels in this regime.