title: Experimental and computational study of HXeY...HX complexes (X, Y = Cl and Br): an example of exceptionally large complexation effect.
abstract: The complexes of xenon hydrides HXeY (Y = Cl and Br) with hydrogen halides HX (X = Cl and Br) have been studied both computationally and experimentally in a xenon matrix. The experiments revealed three new complexes: HXeBr...HBr, HXeBr...HCl, and HXeCl...HCl. The experimental assignments were done on the basis of the strong H-Xe stretching absorption of HXeY (Y = Cl and Br) molecules and supported by theoretical results. We experimentally obtained monomer-to-complex blue-shifts of this vibrational mode for all the studied systems (up to approximately 150 cm (-1)). The electronic structure calculations revealed three local structures for each HNgY...HX complexes and their computed interaction energies varied between -460 and -2800 cm (-1). The computational estimates of the vibrational shifts were in agreement with the experimental values. We also found possible experimental absorption belonging to HXeBr...(HBr) 2 trimer and its vibrational shift (+245 cm (-1)) is similar to the computational estimate of a cyclic ternary complex (+252 cm (-1)).
authors.affiliation: Department of Chemistry, P.O. Box 55, FIN-00014 University of Helsinki, Finland. lignell@csc.fi
authors.forename: Antti
authors.initials: A
authors.lastname: Lignell
authors.forename: Jan
authors.initials: J
authors.lastname: Lundell
authors.forename: Leonid
authors.initials: L
authors.lastname: Khriachtchev
authors.forename: Markku
authors.initials: M
authors.lastname: Räsänen