VUV photochemistry of the H2O center dot center dot center dot CO complex in noble-gas matrices : formation of the OH center dot center dot center dot CO complex and the HOCO radical

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Ryazantsev , S V , Duarte , L , Feldman , V I & Khryachtchev , L 2017 , ' VUV photochemistry of the H2O center dot center dot center dot CO complex in noble-gas matrices : formation of the OH center dot center dot center dot CO complex and the HOCO radical ' , Physical Chemistry Chemical Physics , vol. 19 , no. 1 , pp. 356-365 . https://doi.org/10.1039/c6cp06954a

Title: VUV photochemistry of the H2O center dot center dot center dot CO complex in noble-gas matrices : formation of the OH center dot center dot center dot CO complex and the HOCO radical
Author: Ryazantsev, Sergey V.; Duarte, Luis; Feldman, Vladimir I.; Khryachtchev, Leonid
Contributor: University of Helsinki, Department of Chemistry
University of Helsinki, Department of Chemistry
Date: 2017
Language: eng
Number of pages: 10
Belongs to series: Physical Chemistry Chemical Physics
ISSN: 1463-9076
URI: http://hdl.handle.net/10138/224417
Abstract: Vacuum ultraviolet (VUV, 130-170 nm) photochemistry of the H2O center dot center dot center dot CO complex is studied by matrix-isolation infrared spectroscopy. The H2O center dot center dot center dot CO complexes in Ne, Ar, Kr, and Xe matrices are generated by ultraviolet (UV, 193 and 250 nm) photolysis of formic acid (HCOOH). VUV photolysis of the H2O center dot center dot center dot CO complexes is found to lead to the formation of the OH center dot center dot center dot CO radical-molecule complexes and trans-HOCO radicals. It is shown that the matrix material, local matrix morphology, and possibly the H2O center dot center dot center dot CO complex geometry strongly affect the VUV photolysis pathways. The intrinsic reactivity of the matrix-isolated OH center dot center dot center dot CO complex resulting in the formation of trans-HOCO is directly demonstrated for the first time. This reaction occurs in Ar, Kr, and Xe matrices upon annealing above 25 K and may proceed over the barrier. The case of a Ne matrix is very special because the formation of trans-HOCO from the OH center dot center dot center dot CO complex is observed even at the lowest experimental temperature (4.5 K), which is in sharp contrast to the other matrices. It follows that quantum tunneling is probably involved in this process in the Ne matrix at such a low temperature. Infrared light also promotes this reaction in the Ne matrix at 4.5 K, which is not the case in the other matrices. The last findings show the effect of the environment on the tunneling and infrared-induced rates of this fundamental chemical reaction.
Subject: POTENTIAL-ENERGY SURFACE
CARBON-MONOXIDE COMPLEX
HYDROGEN-BONDED COMPLEXES
LOW-TEMPERATURE MATRICES
INFRARED-LASER SPECTROSCOPY
SOLID ARGON
AB-INITIO
FORMIC-ACID
REACTANT COMPLEX
ATOMIC-HYDROGEN
116 Chemical sciences
114 Physical sciences
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