HIGH-PRESSURE STUDIES OF DYNAMIC SOLVENT EFFECTS ON LARGE AMPLITUDE ISOMERIZATION : 2-(2-PROPENYL)ANTHRACENE
HIGH-PRESSURE STUDIES OF DYNAMIC SOLVENT EFFECTS ON LARGE AMPLITUDE ISOMERIZATION : 2-(2-PROPENYL)ANTHRACENE
复制标题
动态溶剂对大振幅异构化影响的高压研究：2-(2-丙烯基)蒽
DOI：
10.1021/jp962941x
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发表时间：
1997
影响因子：
2.9
通讯作者：
O. Kajimoto
中科院分区：
文献类型：
--
作者：
K. Hara;N. Ito;O. Kajimoto
用稳态和皮秒时间分辨荧光光谱研究了压力对2-(2-丙烯基)菲在一系列烷烃溶剂中激发态异构化速率的影响。利用化学反应的动态溶剂效应理论，分析了异构化反应速率常数对粘度的依赖性。粘度依赖关系比Kramers理论预测的要小得多。用Grote-Hynes理论定义的频变摩擦力对实验结果进行了分析，确定了势垒顶频(ωb)为9.6×10~(12)S~(-1)。
Effect of pressure on the excited-state isomerization rate of 2-(2-propenyl)anthracene in a series of alkane solvents was examined by steady-state and picosecond time-resolved fluorescence spectroscopy. The viscosity dependence of the isomerization rate constant was analyzed by the theories of the dynamic solvent effect on chemical reactions. The viscosity dependence is sufficiently smaller than that predicted by Kramers theory. The experimental result was analyzed by the frequency-dependent friction defined in the Grote-Hynes theory, and the barrier top frequency (ωb ) 9.6 × 1012 s-1) was determined.