Shaw, R.A. and Hill, J. orcid.org/0000-0002-6457-5837 (2018) Midbond basis functions for weakly bound complexes. Molecular Physics, 116 (11). pp. 1460-1470. ISSN 0026-8976
Abstract
Weakly bound systems present a difficult problem for conventional atom-centred basis sets due to large separations, necessitating the use of large, computationally expensive bases. This can be remedied by placing a small number of functions in the region between molecules in the complex. We present compact sets of optimised midbond functions for a range of complexes involving noble gases, alkali metals, and small molecules for use in high accuracy coupled cluster calculations, along with a more robust procedure for their optimisation. It is shown that excellent results are possible with double-zeta quality orbital basis sets when a few midbond functions are added, improving both the interaction energy and the equilibrium bond lengths of a series of noble gas dimers by 47 and 8%, respectively. When used in conjunction with explicitly correlated methods, near complete basis set limit accuracy is readily achievable at a fraction of the cost that using a large basis would entail. General purpose auxiliary sets are developed to allow explicitly correlated midbond function studies to be carried out, making it feasible to perform very high accuracy calculations on weakly bound complexes.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2018 Informa UK Limited, trading as Taylor & Francis Group. This is an author produced version of a paper subsequently published in Molecular Physics. Uploaded in accordance with the publisher's self-archiving policy. |
Keywords: | Midbond functions; explicitly correlated; noncovalent interactions |
Dates: |
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Institution: | The University of Sheffield |
Academic Units: | The University of Sheffield > Faculty of Science (Sheffield) > Department of Chemistry (Sheffield) |
Funding Information: | Funder Grant number ENGINEERING AND PHYSICAL SCIENCE RESEARCH COUNCIL (EPSRC) EP/N00253X/1 |
Depositing User: | Symplectic Sheffield |
Date Deposited: | 08 Feb 2018 12:15 |
Last Modified: | 18 Dec 2020 11:11 |
Status: | Published |
Publisher: | Taylor & Francis |
Refereed: | Yes |
Identification Number: | 10.1080/00268976.2018.1440018 |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:127188 |