Ultraviolet Photodissociation of Gas-Phase Alcohols, Amines, and Nitroalkanes

The 193-nm photochemistry of alcohols, amines, and nitroalkanes in the C3-C6 size range is presented. The photolysis products are photoionized with coherent vacuum ultraviolet radiation and analyzed by time-of-flight mass spectrometry. For alcohols and amines, C-C bond dissociation competes with dissociations involving the heteroatom (C-O, O-H, C-N, N-H). Dissociation of the α(C-C) bond is preferred over other locations. Dissociation of a C-C bond is suppressed when a methyl radical would be produced. This behavior is similar to that observed for other substituted alkanes. Nitroalkanes exhibit both C-N and N-O bond dissociation pathways. Their low bond energies cause a substantial amount of internal energy to be partitioned among the primary photodissociation products. Under collision-free conditions, the alkyl radicals produced from these molecules undergo extensive secondary fragmentation. If the photodissociation step is performed in a free jet expansion, collisional cooling stabilizes the primary products and allows large species, such as intact pentyl and hexyl radicals, to be detected.