Seniority-based coupled cluster theory

TL;DR

This paper introduces a seniority-based coupled cluster approach that extends pCCD by including higher-seniority amplitudes, effectively capturing dynamic correlations in strongly correlated systems with comparable computational cost.

Contribution

It develops a frozen pair coupled cluster method incorporating higher-seniority amplitudes, improving dynamic correlation treatment in strongly correlated systems.

Findings

pCCD accurately reproduces DOCI energies and wave functions.

The extended method is computationally comparable to traditional coupled cluster methods.

Results are competitive for weakly correlated and superior for strongly correlated systems.

Abstract

Doubly occupied configuration interaction (DOCI) with optimized orbitals often accurately describes strong correlations while working in a Hilbert space much smaller than that needed for full configuration interaction. However, the scaling of such calculations remains combinatorial with system size. Pair coupled cluster doubles (pCCD) is very successful in reproducing DOCI energetically, but can do so with low polynomial scaling ($N^3$, disregarding the two-electron integral transformation from atomic to molecular orbitals). We show here several examples illustrating the success of pCCD in reproducing both the DOCI energy and wave function, and show how this success frequently comes about. What DOCI and pCCD lack are an effective treatment of dynamic correlations, which we here add by including higher-seniority cluster amplitudes which are excluded from pCCD. This frozen pair coupled cluster approach is comparable in cost to traditional closed-shell coupled cluster methods with results that are competitive for weakly correlated systems and often superior for the description of strongly correlated systems.