Abstract
Hydrogen sulfide is toxic and corrosive gas abundantly available in nature. The activation of hydrogen sulfide to produce hydrogen and elemental sulfur is of great significance for possible applications in toxic pollutant control and hydrogen energy regeneration. The activation of H(2)S by transition metal atoms (M = Cr, Mn, and Fe) has been studied by low-temperature matrix isolation infrared spectroscopy and quantum chemical calculations. Experimental and theoretical results indicate that the reaction between ground-state M atoms and H(2)S is inhibited by the repulsive interactions between the reactants. After being excited upon photolysis, the corresponding excited-state M atoms react with H(2)S molecules spontaneously. The produced insertion product HMSH further decomposed to metal sulfides upon full-arc mercury lamp irradiation by the splitting of hydrogen.