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dc.contributor.authorHogan, Simon W. L.
dc.contributor.authorVan Mourik, Tanja
dc.date.accessioned2019-12-14T00:36:44Z
dc.date.available2019-12-14T00:36:44Z
dc.date.issued2018-12-14
dc.identifier.citationHogan , 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.25733en
dc.identifier.issn0192-8651
dc.identifier.otherPURE: 256101097
dc.identifier.otherPURE UUID: e1ec560f-ec33-4747-8df1-86d49900ec08
dc.identifier.otherScopus: 85058472683
dc.identifier.otherORCID: /0000-0001-7683-3293/work/57088441
dc.identifier.otherWOS: 000454098000001
dc.identifier.urihttp://hdl.handle.net/10023/19129
dc.descriptionWe thank EastCHEM for support via the EaStCHEM Research Computing Facility.en
dc.description.abstractDensity 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.isoeng
dc.relation.ispartofJournal of Computational Chemistryen
dc.rightsCopyright © 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.25733en
dc.subjectHalogen bonden
dc.subjectHydrogen bonden
dc.subjectHalobenzeneen
dc.subjectDensity functional theoryen
dc.subjectM06-2Xen
dc.subjectQD Chemistryen
dc.subjectNDASen
dc.subject.lccQDen
dc.titleHalogen bonding in mono- and dihydrated halobenzeneen
dc.typeJournal articleen
dc.description.versionPostprinten
dc.description.versionPostprinten
dc.contributor.institutionUniversity of St Andrews.Centre for Research into Equality, Diversity & Inclusionen
dc.contributor.institutionUniversity of St Andrews.EaSTCHEMen
dc.contributor.institutionUniversity of St Andrews.School of Chemistryen
dc.identifier.doihttps://doi.org/10.1002/jcc.25733
dc.description.statusPeer revieweden
dc.date.embargoedUntil2019-12-14


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