Shaw, R.A., Hill, J. orcid.org/0000-0002-6457-5837 and Legon, A.C. (2016) Halogen Bonding with Phosphine: Evidence for Mulliken Inner Complexes and the Importance of Relaxation Energy. The Journal of Physical Chemistry A, 120 (42). pp. 8461-8468. ISSN 1089-5639
Abstract
Intermolecular halogen bonding in complexes of phosphine and dihalogens has been theoretically investigated using explicitly correlated coupled cluster methods and symmetry adapted perturbation theory. The complexes H3P· · · ClF, H3P· · · BrF and H3P· · ·IF are demonstrated to possess unusually strong interactions that are accompanied by an increase in the induction component of the interaction energy and significant elongation of the X–Y halogen distance on complex formation. The combination of these factors is indicative of Mulliken inner complexes and criteria for identifying this classification are further developed. The importance of choosing an electronic structure method that describes both dispersion and longer range interactions is demonstrated, along with the need to account for the change in geometry on complexation formation via relaxation energy and overall stabilisation energies.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2016 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: | 05 Oct 2016 14:53 |
Last Modified: | 04 Oct 2017 01:39 |
Published Version: | http://dx.doi.org/10.1021/acs.jpca.6b08945 |
Status: | Published |
Publisher: | American Chemical Society |
Refereed: | Yes |
Identification Number: | 10.1021/acs.jpca.6b08945 |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:105594 |