A theoretical study of the thermal decomposition of fluoromethanethiol (CH2FSH)

A potential energy surface for the unimolecular decomposition of fluorometh anethiol has been reported at the G2(MP2) level of theory. Eleven product c hannels of CH2FSH were fully detailed. Five possible decomposition pathways of the CH3SF isomer were also examined. The calculations reveal that the f our-center 1,2-HF elimination mechanism rather than the bond scission mecha nism dominates the decomposition of both CH2FSH and CH3SF. The rate coeffic ients of the formation of HF at the high-pressure limit were deduced. The e nthalpies of formation (Delta(f)H(0)(degrees) and Delta(f)H(298)(degrees)) of thirteen sulfur-containing species involved in the CH3SF system were pre dicted at the G2(MP2) level.