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The orbital-specific virtual local triples correction: OSV-L(T)

Schütz, Martin and Yang, Jun and Chan, Garnet Kin-Lic and Manby, Frederick R. and Werner, Hans-Joachim (2013) The orbital-specific virtual local triples correction: OSV-L(T). Journal of Chemical Physics, 138 (5). Art. No. 054109. ISSN 0021-9606.

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A local method based on orbital specific virtuals (OSVs) for calculating the perturbative triples correction in local coupled cluster calculations is presented. In contrast to the previous approach based on projected atomic orbitals (PAOs), described by Schütz [J. Chem. Phys. 113, 9986 (2000)]10.1063/1.1323265, the new scheme works without any ad hoc truncations of the virtual space to domains. A single threshold defines the pair and triple specific virtual spaces completely and automatically. It is demonstrated that the computational cost of the method scales linearly with molecular size. Employing the recommended threshold a similar fraction of the correlation energy is recovered as with the original PAO method at a somewhat lower cost. A benchmark for 52 reactions demonstrates that for reaction energies the intrinsic accuracy of the coupled cluster with singles and doubles excitations and a perturbative treatment of triples excitations method can be reached by OSV-local coupled cluster theory with singles and doubles and perturbative triples, provided a MP2 correction is applied that accounts for basis set incompleteness errors as well as for remaining domain errors. As an application example the interaction energies of the guanine-cytosine dimers in the Watson-Crick and stacked arrangements are investigated at the level of local coupled cluster theory with singles and doubles and perturbative triples. Based on these calculations we propose new complete-basis-set-limit estimates for these interaction energies at this level of theory.

Item Type:Article
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URLURL TypeDescription information
Yang, Jun0000-0001-8701-9297
Chan, Garnet Kin-Lic0000-0001-8009-6038
Manby, Frederick R.0000-0001-7611-714X
Additional Information:© 2013 American Institute of Physics. Received 23 November 2012; accepted 11 January 2013; published online 4 February 2013. G.K.C. acknowledges support from the (U.S.) Department of Energy (DOE), Office of Science Award No. DE-FG02-07ER46432. M.G.S. acknowledges support from the Deutsche Forschungsgemeinschaft (DFG). H.J.W. acknowledges support from the DFG excellence cluster SimTech at the University of Stuttgart.
Funding AgencyGrant Number
Department of Energy (DOE)DE-FG02-07ER46432
Deutsche Forschungsgemeinschaft (DFG)UNSPECIFIED
Subject Keywords:Coupled cluster; Integral transforms; Basis sets; Intermolecular forces; Perturbation theory
Issue or Number:5
Record Number:CaltechAUTHORS:20170125-130249271
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:73723
Deposited By: Donna Wrublewski
Deposited On:25 Jan 2017 23:46
Last Modified:09 Mar 2020 13:19

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