Theoretical treatment of the pressure dependence of the unimolecular rate constant. Part 1.—Cyclobutene, 1-methylcyclobutene and 3-methylcyclobutene

Abstract

The unimolecular rate constants for the thermal isomerizations of cyclobutene, and 1- and 3-methylcyclobutenes have been calculated as functions of pressure using the Marcus-Rice quantum formulation. All vibrational oscillators are assumed to participate in intramolecular energy transfer. The results are compared with the fall-off data for cyclobutene and 3-methyl-cyclobutene and predicted for 1-methyl cyclobutene.