低温下电子在1-丙醇中的脉冲辐射分解研究

J.H. Baxendale, P.H.G. Sharpe
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引用次数: 18

摘要

以前对1-丙醇中电子引起的光谱变化的观测已经扩展到77 K。从118 K到313 K,速率常数符合Tamman和Hesse的修正Arrhenius表达式,从介电色散测量和酒精粘度得到的弛豫时间也符合修正Arrhenius表达式。这些变化被认为是由分子在电子周围重新定向引起的。在118k以下,动力学不再是一阶的,变化在时间上延长得多,也比在较高温度下的观察外推所预期的要快得多。电子损失,假定是由于离子复合,也会发生。得出结论,在这些较低温度下,光谱位移的机制是不同的,这里发生了浅阱的热激发和深阱的再捕获。
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A pulse radiolysis study of electrons in 1-propanol at low temperatures

Previous observations on the spectral changes due to electrons in 1-propanol have been extended to 77 K. It is found that down to 118 K the decay in the I.R. and growth in the visible are first order and that from 118 to 313 K the rate constants fit the modified Arrhenius expression of Tamman and Hesse, as do the relaxation times obtained from dielectric dispersion measurements and the alcohol viscosity. These changes are considered to arise from molecular reorientation around the electrons. Below 118 K, the kinetics are no longer first order, the changes are much more extended in time and are also much faster than expected from an extrapolation of the observations at the higher temperatures. Electron loss, presumed due to ion recombination, also occurs. It is concluded that the mechanism responsible for the spectral shifts is different at these lower temperatures and that here thermal excitation from shallow traps and retrapping by deeper ones occurs.

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