RATE-EQUATIONS FOR THE PHOTOCHEMICAL ISOMERIZATION OF BICYCLOBUTANE

This paper derives and solves the rate equations for several excited states forming several different products. These equations are then applied to bicyclobutane in which the 3P Rydberg states of bicyclobutane were determined in a previous paper to be the progenitors for the photochemical formation of butadiene and cyclobutene. The 1B-1(2) state is deduced to form cis-butadiene and cyclobutene, while the 3(1)A1 and 1B-1(1) states form trans-butadiene. The rate equations are used as a theoretical framework in which to compare computed values with experimental data. Under a set of assumptions, the reaction rates for the formation of these isomers are either calculated or bounded.