Factorized Quadruples and a Predictor of Higher-Level Correlation in Thermochemistry

TL;DR

This paper introduces cost-effective factorized quadruple excitation methods in coupled cluster theory, enabling accurate prediction of reaction energies with significantly reduced computational scaling.

Contribution

It presents a novel factorized CCSD(TQ${}_ ext{f}$) method and a scaled perturbation estimator for efficiently estimating higher-level correlation effects in thermochemistry.

Findings

The factorized CCSD(TQ${}_ ext{f}$) method introduces minimal error compared to traditional methods.

The scaled perturbation estimator predicts CCSDT(Q) contributions with high accuracy.

The approach allows reliable estimation of post-CCSD(T) effects at low computational cost.

Abstract

Coupled cluster theory has had a momentous impact on the ab initio prediction of molecular properties, and remains a staple ingratiate in high-accuracy thermochemical model chemistries. However, these methods require inclusion of at least some connected quadruple excitations, which generally scale at best as $\mathcal{O}(N^9)$ with the number of basis functions. It very difficult to predict, a priori, the effect correlation past CCSD(T) has on a give reaction energies. The purpose of this work is to examine cost-effective quadruple corrections based on the factorization theorem of many-body perturbation theory that may address these challenges. We show that the $\mathcal{O}(N^7)$, factorized CCSD(TQ${}_\text{f}$) method introduces minimal error to predicted correlation and reaction energies as compared to the $\mathcal{O}(N^9)$ CCSD(TQ). Further, we examine the performance of Goodson's continued fraction method in the estimation of CCSDT(Q)${}_\Lambda$ contributions to reaction energies, as well as a "new" method related to %TAE[(T)] that we refer to as a scaled perturbation estimator. We find that the scaled perturbation estimator based upon CCSD(TQ${}_\text{f}$)/cc-pVDZ is capable of predicting CCSDT(Q)${}_\Lambda$/cc-pVDZ contributions to reaction energies with an average error of 0.07 kcal mol${}^{-1}$ and a RMST of 0.52 kcal mol${}^{-1}$ when applied to a test-suite of nearly 3000 reactions. This offers a means by which to reliably ballpark how important post-CCSD(T) contributions are to reaction energies while incurring no more than CCSD(T) formal cost and a little mental math.