Benchmarking the accuracy of seniority-zero wavefunction methods for non-covalent interactions

Abstract

In this paper, we scrutinize the ability of seniority-zero wavefunction-based methods to model different types of non-covalent interactions, such as hydrogen bonds, dispersion, and mixed non-covalent interactions as well as prototypical model systems with various contributions of dynamic and static electron correlation effects. Specifically, we focus on the pair Coupled-Cluster Doubles (pCCD) ansatz combined with two different flavours of dynamic energy corrections, (i) based on a perturbation theory correction and (ii) on a linearized coupled-cluster ansatz on top of pCCD. We benchmark these approaches against the A24 data set [Řez{á}{č} and Hobza, J.~Chem.~Theory~Comput., 9, 2151-2155 (2013)] extrapolated to the basis set limit and some model non-covalent complexes that feature covalent bond breaking. By dissecting different types of interactions in the A24 data set within the Symmetry-Adapted Perturbation Theory (SAPT) framework, we demonstrate that pCCD can be classified as a dispersion-free method. Furthermore, we found that both flavours of post-pCCD approaches represent encouraging and computationally more efficient alternatives to standard electronic structure methods to model weakly-bound systems, resulting in small statistical errors. Finally, a linearized coupled cluster correction on top of pCCD proved to be most reliable for the majority of investigated systems, featuring smaller non-parallelity errors compared to perturbation-theory-based approaches.

arXiv comment16 pages, 10 figures, Version of Record

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• Delving into the Catalytic Mechanism of Molybdenum Cofactors: A Novel Coupled Cluster Study
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