The laser-induced infrared multiphoton isomerization reactions of cis- and trans-1,3,5-hexatriene have been investigated. Excitation of the trans isomer produces vibrationally excited cis molecules possessing sufficient energy to undergo electrocyclic ring closure to 1,3-cyclohexadiene. The ratio of primary (cis) to secondary (cyclohexadiene) products is dependent upon laser fluence and buffer gas pressure. Excitation of the cis isomer produces both trans and cyclohexadiene products. The fluence dependence of the product ratio is in accord with RRKM calculations for competing reactions of the highly excited (70-100 kcal/mol) cis parent isomer.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry