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.

arXiv comment27 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

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Cited by in corpus (12)

• Rank-reduced coupled-cluster III. Tensor hypercontraction of the doubles amplitudes
• Reference Energies for Cyclobutadiene: Automerization and Excited States
• Is Externally Corrected Coupled Cluster Always Better than the Underlying Truncated Configuration Interaction?
• Finite-temperature many-body perturbation theory for electrons: Algebraic recursive definitions, second-quantized derivation, linked-diagram theorem, general-order algorithms, grand canonical and canonical ensembles
• Converging High-Level Coupled-Cluster Energetics via Adaptive Selection of Excitation Manifolds Driven by Moment Expansions
• Benchmarking the Semi-Stochastic CC(P;Q) Approach for Singlet-Triplet Gaps in Biradicals
• Compactification of Determinant Expansions via Transcorrelation
• A hybrid stochastic configuration interaction-coupled cluster approach for multireference systems
• Hilbert space multireference coupled clusters tailored by matrix product states
• High-Level Coupled-Cluster Energetics by Merging Moment Expansions with Selected Configuration Interaction
• The Singlet-Triplet Gap of Cyclobutadiene: The CIPSI-Driven CC($P$;$Q$) Study
• Extension of the CIPSI-Driven CC($P$;$Q$) Approach to Excited Electronic States