Breaking multiple covalent bonds with Hartree-Fock-based quantum chemistry: quasi-variational coupled cluster theory with perturbative treatment of triple excitations

Robinson, James Baden and Knowles, Peter James ORCID: https://orcid.org/0000-0003-4657-6331 2012. Breaking multiple covalent bonds with Hartree-Fock-based quantum chemistry: quasi-variational coupled cluster theory with perturbative treatment of triple excitations. Physical Chemistry Chemical Physics 14 (19) , pp. 6729-6732. 10.1039/c2cp40698e

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Abstract

We enhance the recently proposed Optimized-orbital Quasi-Variational Coupled Cluster Doubles (OQVCCD) method for the calculation of ground-state molecular electronic structure by augmenting it with the standard perturbative (T) correction for the effects of connected triple excitations. We demonstrate the OQVCCD(T) ansatz to be outstandingly robust and accurate in the description of the breaking of the triple bond in diatomic nitrogen, N2, where traditional CCSD and CCSD(T) completely fail, yet with a computational cost that is nearly the same as that of CCSD(T). This result provides insight into the failure of CCSD(T) and related methods and how it may be overcome.

Item Type:	Article
Date Type:	Publication
Status:	Published
Schools:	Advanced Research Computing @ Cardiff (ARCCA) Chemistry
Subjects:	Q Science > QD Chemistry
Publisher:	Royal Society of Chemistry
ISSN:	1463-9076
Date of First Compliant Deposit:	30 March 2016
Last Modified:	16 May 2023 23:22
URI:	https://orca.cardiff.ac.uk/id/eprint/23477

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