Thermal decomposition mechanisms of methylamine, ethylamine, and 1-propylamine on Si(100)-2 x 1 surface

The thermal decomposition reactions of methylamine, ethylamine, and 1-propylamine absorbed on Si(100)-2 x 1 surface were theoretically investigated. Eight decomposition channels were found leading to desorption products of imine, H-2, alkyl cyanide, ammonia, aziridine, alkene, azetidine, and cyclopropane, which supports the experimental assignments. Our mechanistic studies strongly suggest that the alkyl cyanide (hydrogen cyanide in the case of methylamine) channel is coupled with the hydrogen desorption step. The beta-hydrogen of ethylamine and 1-propylamine was found to undergo additional decomposition reactions producing aziridine and alkene, which were classified as gamma- and beta-eliminations, respectively. It was also found that the gamma-hydrogen of 1-propylamine undergoes azetidine and cyclopropane producing decompositions, which were classified as delta- and gamma-eliminations. In general, gamma- and delta-hydrogen involved decomposition reactions are kinetically less favorable than beta-hydrogen involved ones. Consequently, it is expected that the thermal decompositions of the primary alkyl amines with longer alkyl chains would not add additional favorable decomposition channels. Except alkyl cyanide and ammonia desorption channels, the decompositions occur in a concerted fashion. (C) 2011 American Institute of Physics. [doi:10.1063/1.3589362]