超臨界流体中および圧縮液相媒体中の異性化反応における動的溶媒効果

抄録

The viscosity dependence of chemical reactions in solution reveals various aspects of solute-solvent interactions. This paper is concerned with the dynamic solvent effects on isomerizations in solution. The isomerization accompanying large amplitude motion due to bulky atomic groups serves as a prototype for this purpose. The isomerization of 2-vinylanthracene in S₁-excited state has been studied over a wide solvent viscosity range from supercritical fluids to compressed liquids. The “Kramers turnover” behavior has been observed . The turnover region was simulated by a single curve of an additive formula. The dynamic solvent effect on the isomerization accompanied with intramolecular charge-transfer is described by the shift of reaction path, which is called “pressure tuning” effect.