High-Level Coupled-Cluster Energetics by Monte Carlo Sampling and Moment Expansions: Further Details and Comparisons

Abstract

We recently proposed a novel approach to converging electronic energies equivalent to high-level coupled-cluster (CC) computations by combining the deterministic CC($P$;$Q$) formalism with the stochastic configuration interaction (CI) and CC Quantum Monte Carlo (QMC) propagations. This article extends our initial study [J. E. Deustua, J. Shen, and P. Piecuch, Phys. Rev. Lett. 119, 223003 (2017)], which focused on recovering the energies obtained with the CC method with singles, doubles, and triples (CCSDT) using the information extracted from full CI QMC and CCSDT-MC, to the CIQMC approaches truncated at triples and quadruples. It also reports our first semi-stochastic CC($P$;$Q$) calculations aimed at converging the energies that correspond to the CC method with singles, doubles, triples, and quadruples (CCSDTQ). The ability of the semi-stochastic CC($P$;$Q$) formalism to recover the CCSDT and CCSDTQ energies, even when electronic quasi-degeneracies and triply and quadruply excited clusters become substantial, is illustrated by a few numerical examples, including the F-F bond breaking in ${\mathrm{F}}_2$, the automerization of cyclobutadiene, and the double dissociation of the water molecule.

27 pages, 4 tables, 6 figures. Supplementary material as an ancillary file. This article has been accepted for publication in the Journal of Chemical Physics. After it is published, it will be found at https://doi.org/10.1063/5.0045468