High vibrational overtone photochemistry of cyclobutene

Abstract

Direct single-photon excitation of high CH stretching overtone transitions has been used to induce the isomerization of cyclobutene to 1,3-butadiene. Values of the unimolecular isomerization rate constant k(E) have been measured as a function of energy and overtone transition by studying the pressure dependence of the photoisomerization rate constant. The values of k(E) depend on the total energy and do not show any observable dependence on the type of CH overtone transition excited. The values of k(E) are in reasonable quantitative agreement with RRKM calculations. © 1983 American Institute of Physics.