ENERGY TRANSFER IN THE INFRARED LASER-INDUCED REACTION OF METHYL ISOCYANIDE

Article abstract of DOI:10.1021/j100342a037

Experimental results are presented for the infrared laser-induced isomerization of methyl isocyanide to acetonitrile in the presence of several bath gases: Ar, O2, CO2, CH4, C2H6, C2H5CN, C2H5NC, and di-tert-butyl peroxide (DTBP).For all addends except DTBP, increasing the bath gas pressure results in a decrease in acetonitrile yield due to collosional deactivation of the methyl isocyanide.The efficiency of this collosional deactivation is related to the heat capacity and to the vibrational mode distribution of the buffer gas.Ethyl isocyanide as a buffer gas shows an enhanced suppression of the acetonitrile yield due to moderation of the radical channel for the reaction.DTBP, on the other hand, increases the acetonitrile yield and lowers the threshold for massive isomerization due to its generation of methyl radicals.