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Creators: Rasanen, Markku; Pettersson, Mika; Lundell, Jan; Khriachtchev, Leonid
Issue Date: 1997
Publisher: Ohio State University
Abstract: UV-Photolysis of rare gas matrices doped with hydrogen halides yield H and Y (Y=halogen) atoms, and further excitation of the charge-transfer transition of XY pairs (X=Ar,Kr,Xe) results in mobilised holes. Permanent trapping of the holes may occur for instance in centers of type $(XHX)^{+}$. Annealing of the UV-irradiated H-containing matrices results in extremely strong IR-absorptions, which could by doping experiments be shown to belong to neutral species of type HXY. The novel rare-gas containing species found so far are HXeCl, HXeBr, HXeI, HKrCl and HXeH. All these species are strongly polar and their common structure is $(HX)^{+}Y^{-}$. In order to learn more about the potential surface, detailed spectroscopic studies are performed on HXel. This species can be photodecomposed into neutral atoms by infrared irradiation in the $3 \mu m$ region, and recovered quantitatively thermally at temperatures below 30 K. An Arrhenius analysis propose for the barrier from neutral atoms to HXel a value of $700 cm^{-1}$. We suggest that this barrier originates from an avoided crossing between two singlet surfaces limiting either to separated atoms H + Xe + I or to ionic species $(HXe)^{+} I^{-}$.
Description: References: Neutral rare-gas containing charge-transfer molecules in solid matrices. I. HXeCl, HXeBr, HXel and HKrCl in Kr and Xe. M.Pettersson, J.Lundell, M.R\""as\""anen, {J.Chem.Phys}. 102 (1995) 6423-31. Neutral rare gas containing charge-transfer molecules in solid matrices. II. HXeH, HXeD and DXeD in Xe. M.Pettersson, J.Lundell, M.R\""as\""anen, {J.Chem.Phys}. 103 (1995) 205-10. The mechanism of formation and IR-induced decomposition of HXel in solid Xe. M.Pettersson, J.Nieminen, L.Khriachtchev, M.R\""as\""anen, {J.Chem.Phys. to be submitted}.
Author Institution: Laboratory of Physical Chemistry, University of Helsinki
Other Identifiers: 1997-TH-07
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