On photochemistry of water in solid Xe: Thermal and light-induced decomposition of HXeOH and HXeH and formation of H2O2

A photochemical study of water (H2 16O, H2 18O, D2 16O, and D2 18O) in solid Xe is described. The water–Xe samples were irradiated at 193 nm and then annealed at 40–50 K, which led to formation of various isotopomers of Xe-containing molecules, HXeOH and HXeH. This diffusion-controlled formation of HXeH and HXeOH consumes the main part of hydrogen atoms generated in the matrix during photolysis. Both photodecomposition profiles and ultraviolet (UV) absorption spectra of HXeOH and HXeH feature a broad absorption band of these species around 240 nm corresponding to the transition to the repulsive excited states. It is also found that HXeOH and HXeH molecules can be thermally destroyed in similar time scales of ∼10 min at about 54 and 66 K, respectively. This clear difference between the decomposition temperatures for HXeOH and HXeH suggests the intrinsic basis of the decomposition process, which possibly occurs over the barriers of the bending coordinates. The absence of strong H–D isotope effect in this thermal decomposition indicates that tunneling of hydrogen is not essentially involved in the process at these temperatures. However, the local disorder of a Xe matrix seems to produce inhomogeneous broadening of the activation energies of the decomposition as indicated by the observed nonexponential decay kinetics. Upon photolysis and annealing of the H2O–Xe samples, monomeric and complexed hydrogen peroxide is formed originating, at least partially, from water clusters stabilized in solid Xe. In addition, we report the vibrational data on various isotopomers of HXeH, HXeOH, H2O, OH, and OH⋯H2O isolated in solid Xe.