Formation of noble-gas hydrides and decay of solvated protons revisited: diffusion-controlled reactions and hydrogen atom losses in solid noble gases

Abstract

UV photolysis and annealing of C₂H₂/Xe, C₂H₂/Xe/Kr, and HBr/Xe matrices lead to complicated photochemical processes and reactions. The dominating products in these experiments are noble-gas hydrides with general formula HNgY (Ng = noble-gas atom, Y = electronegative fragment). We concentrate on distinguishing the local and global mobility and losses of H atoms, barriers of the reactions, and the decay of solvated protons. Different deposition temperatures change the amount of lattice imperfections and thus the amount of traps for H atoms. The averaged distance between reacting species influencing the reaction kinetics is controlled by varying the precursor concentration. A number of solid-state processes connected to the formation of noble-gas hydrides and decay of solvated protons are discussed using a simple kinetic model. The most efficient formation of noble-gas hydrides is connected with global (long-range) mobility of H atoms leading to the H + Xe + Y reaction. The highest concentration of noble-gas hydrides was obtained in matrices of highest optical quality, which probably have the lowest concentration of defects and H-atom losses. In matrices with high amount of geometrical imperfections, the product formation is inefficient and dominated by a local (short-range) process. The decay of solvated protons is rather local than a global process, which is different from the formation of noble-gas molecules. However, the present data do not allow distinguishing local proton and electron mobilities. Our previous results indicate that these are electrons which move to positively-charged centers and neutralize them. It is believed that the image obtained here for solid xenon is applicable to solid krypton whereas the case of argon deserves special attention.