Implications for multidimensional effects on isomerization dynamics: Photoisomerization study of 4,4′-dimethylstilbene in n-alkane solvents

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Abstract
Studies of the photoisomerization of 4,4’‐dimethylstilbene in n‐alkane solvents are reported. As with similar studies it is possible to identify an activation barrier to isomerization and the viscosity dependence of the isomerization is not adequately explained by a one‐dimensional hydrodynamic Kramers equation. Comparison of the isomerization rates with those of other stilbenes suggests that the use of a frequency dependent friction for the solvent does not consistently explain the data. These results and those of other stilbenes can be explained by a two‐dimensional isomerization coordinate where the reaction trajectory is linked to the solvent viscosity.