Hill, J. orcid.org/0000-0002-6457-5837 and Legon, A.C. (2019) Nonbonding pairs in cyclic thioethers: Electrostatic modelling and ab initio calculations for complexes of 2,5-dihydrothiophene, thietane and thiirane with hydrogen fluoride. International Journal of Quantum Chemistry, 119 (10). e25885. ISSN 0020-7608
Abstract
Electrostatic potential energies V(ϕ) of a non‐perturbing, protonic charge at fixed distances r from the S atom in three cyclic thioethers were examined as functions of the angles ϕ made by the r‐vector with the C2 axis (thiirane and 2,5‐dihydrothiophene) or the local C2 axis (thietane). The electrostatic PE VHF(ϕ) of HF (HF modelled as an extended electric dipole) was also calculated and the results compared with geometries of the thioether⋯HF complexes calculated at the CCSD(T)‐F12c/cc‐pVTZ‐F12 level. The latter reveal angular deviations θ ∼10‐20° of the S⋯H-F nuclei from collinearity in directions suggesting secondary interactions of F with H atom(s) of the rings. Angles ϕ made by the S⋯H hydrogen bond with the C2 (or local C2) axes in the complexes are systematically larger (∼4‐9°) than indicated by the VHF(ϕ) functions. Minima in the simple V(ϕ) versus ϕ functions occur at values smaller (∼5‐10°) than those in the VHF(ϕ) curves.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2018 Wiley Periodicals, Inc. This is an author produced version of a paper subsequently published in International Journal of Quantum Chemistry. Uploaded in accordance with the publisher's self-archiving policy. |
Dates: |
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Institution: | The University of Sheffield |
Academic Units: | The University of Sheffield > Faculty of Science (Sheffield) > Department of Chemistry (Sheffield) |
Depositing User: | Symplectic Sheffield |
Date Deposited: | 18 Dec 2018 09:58 |
Last Modified: | 24 Nov 2021 08:59 |
Status: | Published |
Publisher: | Wiley |
Refereed: | Yes |
Identification Number: | 10.1002/qua.25885 |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:139795 |