Kinetic Studies of the Pulse Radiolysis of trans-Stilbem in Several Solvents

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The kinetics of the transient species of trans-stilbene in several solvents were studied using single pulsed electron beam (0.5 μsec×300 mA) and the spectroscopic method. The species existing immediately (0–20μsec) after a pulse is found to disappear according to a sum of two first-order decay-rate equations. The temperature dependence of the formation and decay of this species shows that there are two different trans-stilbene cations, Rs and Rf, which have almost identical absorption spectra but different formation and decay rates. The rate constants for Rs were not affected by the temperature, however, those for Rf were strongly affected. Rf is not found in the solution of trans-stilbene in 1,2-dichloroethane if a small amount of CCl4 is added. Some effects of the dielectric constant were observed on the decay-rate constant of Rf. From these facts, it can be concluded that Rf is formed by an ordinary transfer of a hole from the solvent cation to the solute molecule. As Rs seems to be formed by a mechanism other than that of Rf, a possible scheme for it has been discussed.
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