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Title: Environmental effects on noble-gas hydrides: HXeBr, HXeCCH, and HXeH in noble-gas and molecular matrices

Noble-gas hydrides HNgY (Ng is a noble-gas atom and Y is an electronegative group) are sensitive probes of local environment due to their relatively weak bonding and large dipole moments. We experimentally studied HXeBr in Ar, Kr, and N{sub 2} matrices, HXeCCH in Ne and N{sub 2} matrices, and HXeH in an N{sub 2} matrix. These are the first observations of noble-gas hydrides in an N{sub 2} matrix. An N{sub 2} matrix strongly increases the H–Xe stretching frequency of HXeBr and HXeCCH with respect to a Ne matrix, which is presumably due to a strong interaction between the HNgY dipole moment and quadrupole moments of the surrounding lattice N{sub 2} molecules. The spectral shift of HXeBr in an N{sub 2} matrix is similar to that in a CO{sub 2} matrix, which is a rather unexpected result because the quadrupole moment of CO{sub 2} is about three times as large as that of N{sub 2}. The H–Xe stretching frequencies of HXeBr and HXeCCH in noble-gas matrices show a trend of ν(Ne) < ν(Xe) < ν(Kr) < ν(Ar), which is a non-monotonous function of the dielectric constants of the noble-gas solids. The MP2(full) calculations of HXeBr and HXeCCH with the polarizable continuummore » model as well as the CCSD(T) calculations of the HXeBr···Ng and HXeCCH···Ng (Ng = Ne, Ar, Kr, and Xe) complexes cannot fully explain the experimental observations. It is concluded that more sophisticated computational models should be used to describe these experimental findings.« less
Authors:
; ; ;  [1]
  1. Department of Chemistry, University of Helsinki, P.O. Box 55, FIN-00014 (Finland)
Publication Date:
OSTI Identifier:
22253988
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 139; Journal Issue: 20; Other Information: (c) 2013 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 54 ENVIRONMENTAL SCIENCES; CARBON DIOXIDE; COMPUTER CALCULATIONS; CRYSTAL LATTICES; DIPOLE MOMENTS; ENVIRONMENTAL EFFECTS; HYDRIDES; QUADRUPOLE MOMENTS; RARE GASES; SIMULATION; SOLIDS; STRONG INTERACTIONS