Coupled electron pair-type approximations for tensor product state wavefunctions

TL;DR

This paper introduces a tensor product state (TPS) based extension of CEPA methods, which removes singularities and improves accuracy in strongly correlated systems, outperforming traditional determinant-based approaches.

Contribution

The authors develop a TPS-based formulation of CEPA methods that addresses singularities and enhances accuracy for strongly correlated molecules.

Findings

TPS-CEPA removes singularities present in traditional CEPA methods.

TPS-CEPA provides more accurate results for bond breaking and conjugated systems.

The method outperforms standard electronic structure approaches in tested cases.

Abstract

Size extensivity, defined as the correct scaling of energy with system size, is a desirable property for any many-body method. Traditional CI methods are not size extensive hence the error increases as the system gets larger. Coupled electron pair approximation (CEPA) methods can be constructed as simple extensions of truncated configuration interaction (CI) that ensures size extensivity. One of the major issues with the CEPA and its variants is that singularities arise in the amplitude equations when the system starts to be strongly correlated. In this work, we extend the traditional Slater determinant-based coupled electron pair approaches like CEPA-0, averaged coupled-pair functional (ACPF) and average quadratic coupled-cluster (AQCC) to a new formulation based on tensor product states (TPS). We show that a TPS basis can often be chosen such that it removes the singularities that commonly destroy the accuracy of CEPA-based methods. A suitable TPS representation can be formed by partitioning the system into separate disjoint clusters and forming the final wavefunction as the tensor product of the many body states of these clusters. We demonstrate the application of these methods on simple bond breaking systems such as CH$_4$ and F$_2$ where determinant based CEPA methods fail. We further apply the TPS-CEPA approach to stillbene isomerization and few planar $\pi-$conjugated systems. Overall the results show that the TPS-CEPA method can remove the singularities and provide improved numerical results compared to common electronic structure methods.