Effect of the structural nonequilibrium of solid samples on the low temperature limit of the photochemical reaction rate

Abstract

The results from two cryogenic experiments at helium temperatures are compared. Widely separated and adjacent aggregations formed by vapor deposition are considered. It is shown that upon the photochlorination of methane in a solid structural nonequilibrium mixture prepared from the gas phase at liquid helium temperatures, the quantum yield of chlorine consumption at the low temperature limit falls to zero while the effective activation energy in the Arrhenius region rises due to achieving a state of supersaturation with vacancies and a vibrational mode of sintering. It is demonstrated that upon the photobromination of ethylene under conditions of disequilibrium decay, accompanied by halogen-olefin self-organization of the condensate structure (complexation), the quantum yield of bromine consumption in the athermal region rises while the activation energy in the Arrhenius region falls.