Abstract
Measurements of laser-pulse-induced transient optical absorptions and transient electrical and conductance reveal that excitation of 4- N,N-dimethylaminobenzonitrile and related compounds in acetonitrile or water at 308 nm leads to formation of radical cations of the solutes. In acetonitrile the cations are formed in a single-photon process via a singlet state solute-solvent exciplex, whereas in water they are formed mainly by a biphotonic process. It follows from the transient absorptions of the compounds in cyclohexane, 1,4-dioxane and acetonitrile that the solutes in their lowest electronic triplet state do not form exciplexes with these solvents.
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