Single reference treatment of strongly correlated H$_4$ and H$_{10}$ isomers with Richardson-Gaudin states

TL;DR

This paper demonstrates that Richardson-Gaudin states can effectively describe strongly correlated H4 and H10 isomers with a single reference, offering a new approach for modeling complex electron correlations.

Contribution

The study introduces the use of Richardson-Gaudin states as a variational wavefunction for strongly correlated isomers, showing their effectiveness compared to traditional pair theories.

Findings

RG states describe seniority-zero sector well

Simple orbital functionals approximate weak correlation

RG-based CI improves systematic accuracy

Abstract

Richardson-Gaudin (RG) states are employed as a variational wavefunction ansatz for strongly correlated isomers of H$_4$ and H$_{10}$. In each case a single RG state describes the seniority-zero sector quite well. Simple natural orbital functionals offer a cheap and reasonable approximation of the outstanding weak correlation in the seniority-zero sector, while systematic improvement is achieved by performing a configuration interaction (CI) in terms of RG states. Other pair theories (e.g. generalized valence bond and pair-coupled-cluster doubles) can provide a good description of many of the geometries considered, but, at short distances, the wavefunctions for the 2D and 3D structures of H$_{10}$ take the form of an RG state that cannot be described by these other theories.