Picosecond dynamics of barrier crossing in solution: A study of the conformational change of excited state 1,1’‐binaphthyl
Picosecond dynamics of barrier crossing in solution: A study of the conformational change of excited state 1,1’‐binaphthyl
复制标题
溶液中势垒穿越的皮秒动力学：激发态1,1-联萘构象变化的研究
DOI：
10.1063/1.449721
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发表时间：
1985
期刊：
影响因子：
--
通讯作者：
K. Eisenthal
中科院分区：
文献类型：
--
作者：
D. Millar;K. Eisenthal
用皮秒激光技术测量了1，1 '-联萘在一系列醇溶剂中的光诱导构象变化速率。Kramers模型的中间和高摩擦制度使用的频率无关的摩擦系数从经典流体力学评价与实验的良好协议。这是第一次观察到的Kramers行为在中间摩擦制度，并表明偏离Kramers行为是不是一个普遍的现象，在溶液中的柔性分子的构象动力学。它还强调了观察到的与Kramers模型的偏差可能是由于非马尔可夫摩擦以外的影响。
The rates of optically induced conformational changes of excited state 1,1’‐binaphthyl in a series of alcohol solvents were measured by a picosecond laser technique. Excellent agreement with experiment is found for the Kramers model for both the intermediate and high friction regimes using a frequency independent friction coefficient evaluated from classical hydrodynamics. This is the first observation of Kramers behavior in the intermediate friction regime and indicates that deviations from Kramers behavior is not a universal phenomenon in the conformational dynamics of flexible molecules in solution. It also emphasizes the possibility that the observed deviations from the Kramers model can be due to effects other than non‐Markovian friction.