Approximate variational coupled cluster theory

Robinson, James B. and Knowles, Peter James ORCID: https://orcid.org/0000-0003-4657-6331 2011. Approximate variational coupled cluster theory. Journal of Chemical Physics 135 (4) , 044113. 10.1063/1.3615060

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Abstract

We show that it is possible to construct an accurate approximation to the variational coupled cluster method, limited to double substitutions, from the minimization of a functional that is rigorously extensive, exact for isolated two-electron subsystems and invariant to transformations of the underlying orbital basis. This approximate variational coupled cluster theory is a modification and enhancement of our earlier linked pair functional theory. It is first motivated by the constraint that the inverse square root of the matrix that transforms the cluster amplitudes must exist. Low-order corrections are then included to enhance the accuracy of the approximation of variational coupled cluster, while ensuring that the computational complexity of the method never exceeds that of the standard traditional coupled cluster method. The effects of single excitations are included by energy minimization with respect to the orbitals defining the reference wavefunction. The resulting quantum chemical method is demonstrated to be a robust approach to the calculation of molecular electronic structure and performs well when static correlation effects are strong.

Item Type:	Article
Date Type:	Publication
Status:	Published
Schools:	Chemistry
Subjects:	Q Science > QC Physics Q Science > QD Chemistry
Uncontrolled Keywords:	approximation theory, coupled cluster calculations, minimisation, molecular electronic states, variational techniques, wave functions
Additional Information:	9 pages. Pdf uploaded in accordance with publisher's policy at http://www.sherpa.ac.uk/romeo/issn/0021-9606/ (accessed 21/02/2014).
Publisher:	American Institute of Physics
ISSN:	0021-9606
Date of First Compliant Deposit:	30 March 2016
Last Modified:	04 May 2023 00:45
URI:	https://orca.cardiff.ac.uk/id/eprint/11319

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