Hill, J.G. orcid.org/0000-0002-6457-5837 and Legon, A.C. (2022) Radial potential energy functions of linear halogen-bonded complexes YX…ClF, (YX = FB, OC, SC, N2) and the effects of substituting X by second-row analogues : Mulliken inner and outer complexes. Journal of Physical Chemistry A, 126 (16). pp. 2511-2521. ISSN 1089-5639
Abstract
Energies of linear, halogen-bonded complexes in the isoelectronic series YX...ClF (YX = FB, OC or N2) are calculated at several levels of theory as a function of the intermolecular distance r(X...Cl) to yield radial potential energy functions. When YX = OC, a secondary minimum was observed corresponding to lengthened and shortened distances r(ClF) and r(CCl), respectively, relative to the primary minimum, suggesting a significant contribution from the Mulliken inner complex structure [O=C–Cl]+...F. A conventional weak, halogen-bond complex OC...ClF occurs at the primary minimum. For YX = FB, the primary minimum corresponds to the inner complex [F=B–Cl]+...F-, while the outer complex FB...ClF is at the secondary minimum. The effects on the potential energy function of systematic substitution of Y and X by second row congeners and of reversing the order of X and Y are also investigated. Symmetry adapted perturbation theory and natural population analyses are applied to further understand the nature of the various halogen-bond interactions.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2022 American Chemical Society. This is an author-produced version of a paper subsequently published in Journal of Physical Chemistry A. 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: | 06 Apr 2022 14:06 |
Last Modified: | 15 Apr 2023 00:13 |
Status: | Published |
Publisher: | American Chemical Society |
Refereed: | Yes |
Identification Number: | 10.1021/acs.jpca.2c01205 |
Related URLs: | |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:185193 |