The Dose Makes the Poison: Perturbative Steps Toward the Ultimate Linearized Coupled Cluster Method

TL;DR

This paper introduces xlinCCD(2), a linearized coupled cluster method that corrects for dynamical correlation deficiencies in linLCCD, making it more accurate and regular for weakly-correlated systems.

Contribution

It develops a second-order correction to linearized CC methods, improving their accuracy while maintaining computational efficiency.

Findings

xlinCCD(2) is regular and avoids divergences.

xlinCCD(2) yields results comparable to linearized CCD in weakly-correlated regimes.

The method effectively adds dynamical correlation corrections.

Abstract

"Addition-by-subtraction" coupled cluster (CC) approaches provide a promising approach to treating the difficult strong correlation problem by simplifying the standard CC equations. In a separate vein, linearized CC methods have drawn interest for their lower computational cost, increased parallelizability, and favorable properties for extension to the excited state--but the inclusion of ring/crossed-ring terms causes singularities even for single bond breaking. A linearized, addition-by-subtraction CC method called linearized ladder CCD (linLCCD) removes these terms to avoid divergences, but linLCCD under-estimates dynamical correlation. Herein we resolve this deficiency of linLCCD by introducing a linearized external coupled cluster perturbation theory that adds a second-order ring/crossed-ring correction back into a linLCCD reference wave function. Our resultant xlinCCD(2) method is regular and yields comparable results to linearized CCD in weakly-correlated regimes.