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Halogen bonding in mono- and dihydrated halobenzene
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dc.contributor.author | Hogan, Simon W. L. | |
dc.contributor.author | Van Mourik, Tanja | |
dc.date.accessioned | 2019-12-14T00:36:44Z | |
dc.date.available | 2019-12-14T00:36:44Z | |
dc.date.issued | 2018-12-14 | |
dc.identifier.citation | Hogan , S W L & Van Mourik , T 2018 , ' Halogen bonding in mono- and dihydrated halobenzene ' , Journal of Computational Chemistry , vol. Early View . https://doi.org/10.1002/jcc.25733 | en |
dc.identifier.issn | 0192-8651 | |
dc.identifier.other | PURE: 256101097 | |
dc.identifier.other | PURE UUID: e1ec560f-ec33-4747-8df1-86d49900ec08 | |
dc.identifier.other | Scopus: 85058472683 | |
dc.identifier.other | ORCID: /0000-0001-7683-3293/work/57088441 | |
dc.identifier.other | WOS: 000454098000001 | |
dc.identifier.uri | https://hdl.handle.net/10023/19129 | |
dc.description | We thank EastCHEM for support via the EaStCHEM Research Computing Facility. | en |
dc.description.abstract | Density functional theory calculations were performed on halogen-bonded and hydrogen-bonded systems consisting of a halobenzene (XPh; X = F, Cl, Br, I, At) and one or two water molecules, using the M06-2X density functional with the 6-31+G(d) (for C, H, F, Cl, Br) and aug-cc-pVDZ-PP (for I, At) basis sets. The counterpoise procedure was performed to counteract the effect of basis set superposition error. The results show halogen bonds form in the XPh-H2O system when X > Cl. There is a trend towards stronger halogen bonding as the halogen group is descended, as assessed by interaction energy and X•••Ow internuclear separation (where Ow is the water oxygen). For all XPh-H2O systems hydrogen-bonded systems exist, containing a combination of CH•••Ow and OwHw•••X hydrogen bonds. For all systems except X=At the X•••Hw hydrogen-bonding interaction is stronger than the X•••Ow halogen bond. In the XPh-(H2O)2 system halogen bonds form only for X > Br. The two water molecules prefer to form a water dimer, either located around the C-H bond (for X = Br, At, and I) or located above the benzene ring (for all halogens). Thus, even in the absence of competing strong interactions, halogen bonds may not form for the lighter halogens due to (i) competition from cooperative weak interactions such as C-H•••O and OH•••X hydrogen bonds, or (ii) if the formation of the halogen bond would preclude the formation of a water dimer. | |
dc.language.iso | eng | |
dc.relation.ispartof | Journal of Computational Chemistry | en |
dc.rights | Copyright © 2018 Wiley Periodicals, Inc. This work has been made available online in accordance with the publisher’s policies. This is the author created, accepted version manuscript following peer review and may differ slightly from the final published version. The final published version of this work is available at: https://doi.org/10.1002/jcc.25733 | en |
dc.subject | Halogen bond | en |
dc.subject | Hydrogen bond | en |
dc.subject | Halobenzene | en |
dc.subject | Density functional theory | en |
dc.subject | M06-2X | en |
dc.subject | QD Chemistry | en |
dc.subject | NDAS | en |
dc.subject.lcc | QD | en |
dc.title | Halogen bonding in mono- and dihydrated halobenzene | en |
dc.type | Journal article | en |
dc.description.version | Postprint | en |
dc.description.version | Postprint | en |
dc.contributor.institution | University of St Andrews. Centre for Research into Equality, Diversity & Inclusion | en |
dc.contributor.institution | University of St Andrews. EaSTCHEM | en |
dc.contributor.institution | University of St Andrews. School of Chemistry | en |
dc.identifier.doi | https://doi.org/10.1002/jcc.25733 | |
dc.description.status | Peer reviewed | en |
dc.date.embargoedUntil | 2019-12-14 |
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