Decomposition of chemically activated dimethylcyclopropane molecules vibrationally excited to various extent

The photolyses of ketene (at 313 and 280 nm) and diazirine at 313 nm in the presence of cis-butene-2 were studied. Vibrational relaxation of chemically activated dimethylcyclopropane was shown to occur as a multistep process, and 17 ± 4 kJ mol^?1 was obtained for the average energy transferred per collision with butene-2 collider. Activated cis-dimethylcyclopropane is formed in the reaction of singlet methylene and cis-butene-2 with broad energy distribution which originates from the energy partitioning in the photolytic act. About 30% of the energy released in the photolysis of the methylene source is carried by singlet methylene as vibrational energy at the time of reaction, and this fraction was found to be practically independent of the radical source.