Real-time observation of the photoionization-induced water rearrangement dynamics in the 5-hydroxyindole-water cluster by time-resolved IR spectroscopy.
Real-time observation of the photoionization-induced water rearrangement dynamics in the 5-hydroxyindole-water cluster by time-resolved IR spectroscopy.
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通过时间分辨红外光谱实时观察5-羟基吲哚-水簇中光电离诱导的水重排动力学
DOI：
10.1039/c7cp06127g
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发表时间：
2018
期刊：
影响因子：
--
通讯作者：
M. Fujii
中科院分区：
文献类型：
--
作者：
M. Miyazaki;A. Naito;T. Ikeda;J. Klyne;K. Sakota;H. Sekiya;O. Dopfer;M. Fujii
溶剂化在控制溶液中化学反应的机理和动力学方面起着至关重要的作用。本研究揭示了局部溶质-溶剂相互作用的变化对溶剂重排动力学的时间尺度有很大的影响。时间分辨红外光谱已被应用到一水合5-羟基吲哚-水簇的溶质分子的光电离诱导的水合重排反应。水分子将稳定的水合位点从吲哚NH位点改变为取代基OH位点，这两者都提供了强烈的水合吸引力。重排时间常数为8 ± 2 ns，并且在较低的过剩能量下进一步减慢超过5倍。这些重排时间慢约三个数量级，比那些报道的相关系统，其中水分子被排斥的相互作用势的排斥部分朝着一个有吸引力的井。RRKM理论很好地再现了时间常数与过剩能量的关系。在能量弛豫动力学的基础上讨论了反应机理的差异。
Solvation plays an essential role in controlling the mechanism and dynamics of chemical reactions in solution. The present study reveals that changes in the local solute–solvent interaction have a great impact on the timescale of solvent rearrangement dynamics. Time-resolved IR spectroscopy has been applied to a hydration rearrangement reaction in the monohydrated 5-hydroxyindole–water cluster induced by photoionization of the solute molecule. The water molecule changes the stable hydration site from the indolic NH site to the substituent OH site, both of which provide a strongly attractive potential for hydration. The rearrangement time constant amounts to 8 ± 2 ns, and is further slowed down by a factor of more than five at lower excess energy. These rearrangement times are slower by about three orders of magnitude than those reported for related systems where the water molecule is repelled from a repulsive part of the interaction potential toward an attractive well. The excess energy dependence of the time constant is well reproduced by RRKM theory. Differences in the reaction mechanism are discussed on the basis of energy relaxation dynamics.
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芳香族分子范德华配合物的动力学和结构
DOI：
--
发表时间：
1993
期刊：
影响因子：
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作者：
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作者：
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DOI：
10.1063/1.1668640
发表时间：
2004-04
期刊：
The Journal of chemical physics
影响因子：
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作者：
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