Shaw, R.A. and Hill, J.G. orcid.org/0000-0002-6457-5837 (2017) Approaching the Hartree-Fock Limit Through the CABS Singles Correction and Auxiliary Basis Sets. Journal of Chemical Theory and Computation, 13 (4). pp. 1691-1698. ISSN 1549-9618
Abstract
Auxiliary basis sets for use in the resolution of the identity (RI) approximation in explicitly correlated methods are presented for the elements H–Ar. These extend the cc-pVnZ-F12/OptRI (n = D–Q) auxiliary basis sets of Peterson and coworkers by the addition of a small number of s- and p-functions, optimized so as to yield the great- est complementary auxiliary basis set (CABS) singles correction to the Hartree-Fock energy. The new sets, denoted OptRI+, also lead to a reduction in errors due to the RI approximation and hence an improvement in correlation energies. The atomization energies and heats of formation for a test set of small molecules, and spectroscopic constants for 27 diatomics, calculated at the CCSD(T)-F12b level, are shown to have improved error distributions for the new auxiliary basis sets with negligible additional effort. The OptRI+ sets retain all of the desirable properties of the original OptRI, including the production of smooth potential energy surfaces, whilst maintaining a compact nature.
Metadata
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Copyright, Publisher and Additional Information: | © 2017 American Chemical Society. This is an author produced version of a paper subsequently published in Journal of Chemical Theory and Computation. Uploaded in accordance with the publisher's self-archiving policy. | ||||
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Institution: | The University of Sheffield | ||||
Academic Units: | The University of Sheffield > Faculty of Science (Sheffield) > Department of Chemistry (Sheffield) | ||||
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Depositing User: | Symplectic Sheffield | ||||
Date Deposited: | 03 Mar 2017 16:51 | ||||
Last Modified: | 28 Feb 2018 01:38 | ||||
Published Version: | https://doi.org/10.1021/acs.jctc.7b00140 | ||||
Status: | Published | ||||
Publisher: | American Chemical Society | ||||
Refereed: | Yes | ||||
Identification Number: | https://doi.org/10.1021/acs.jctc.7b00140 |