Benchmarking the Semi-Stochastic CC(P;Q) Approach for Singlet-Triplet Gaps in Biradicals

Abstract

We recently proposed a semi-stochastic approach to converging high-level coupled-cluster (CC) energetics, such as those obtained in the CC calculations with singles, doubles, and triples (CCSDT), in which the deterministic CC($P$;$Q$) framework is merged with the stochastic configuration interaction Quantum Monte Carlo propagations [J. E. Deustua, J. Shen, and P. Piecuch, Phys. Rev. Lett. 119, 223003 (2017)]. In this work, we investigate the ability of the semi-stochastic CC($P$;$Q$) methodology to recover the CCSDT energies of the lowest singlet and triplet states and the corresponding singlet-triplet gaps of biradical systems using methylene, ${(\mathrm{HFH})}^{-}$, cyclobutadiene, cyclopentadienyl cation, and trimethylenemethane as examples.

28 pages, 7 tables, 5 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/10.1063/5.0100165

References in corpus (5)

• Unbiasing the initiator approximation in Full Configuration Interaction Quantum Monte Carlo
• The Adaptive Shift Method in Full Configuration Interaction Quantum Monte Carlo: Development and Applications
• Reference Energies for Cyclobutadiene: Automerization and Excited States
• Accurate singlet-triplet gaps in biradicals via the spin averaged anti-Hermitian contracted Schrödinger equation
• High-Level Coupled-Cluster Energetics by Monte Carlo Sampling and Moment Expansions: Further Details and Comparisons

Cited by in corpus (4)

• Coupled cluster theory: Towards an algebraic geometry formulation
• Converging High-Level Coupled-Cluster Energetics via Adaptive Selection of Excitation Manifolds Driven by Moment Expansions
• 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