Femtosecond studies of the iodine–mesitylene charge-transfer complex

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Abstract
Femtosecond laser studies have been performed to investigate the initial photodissociation reactions of I2–mesitylene charge transfer complexes. Photodissociation occurs along both the I2–mesitylene ‘‘bond’’ and the I–I bond with a branching ratio of 2:3 for the two reaction coordinates. Following excitation at 400 nm, geminate recombination occurs along both reaction coordinates. The reformed I2–mesitylene complexes are formed vibrationally hot and relax on a time scale of 13 ps. The I–mesitylene spectrum is fully developed within 500 fs of the pump pulse. Approximately 40% of the I–mesitylene complexes undergo geminate recombination on a time scale of 14 ps. Most of the remaining complexes recombine with their original partners on a time scale of 400 ps. The initial anisotropy of the photoproduct absorption is 0.09±0.02. This low anisotropy is a direct result of the geometry of the complex and nature of the electronic transition rather than indicative of ultrafast motion toward an asymmetric transition state preceding dissociation.

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