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首页> 外文期刊>Chemistry: A European journal >Solvation of Radical Cations in Water-Reactive or Unreactive Solvation?
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Solvation of Radical Cations in Water-Reactive or Unreactive Solvation?

机译：在水反应性或非反应性溶剂化中的自由基阳离子的溶剂化？

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The solvation and reaction of ethylene radical cation in aqueous solution has been studied with Car-Parrinello molecular dynamics simulations. All ab initio simulations were performed using a systgem of 56 water and one ethylene moilecule. Using a favorable ethylene molecule. Using a favorable symmetrically solvented radical cation as the starting point of the simulation a fast addition of water (within 90 fs) to the radical cation is observed. The primary addition product is rapidly deprotonated (within 100 fs) to yield the ethanol-2-yl radical. A second simulation was initiated through vertical ionization of neutral hydrated ethylene, representing a significantly less favorable situation for the addition process. No addition of water can be observed in this second simulation over a time span of 1.7 ps. Taken together the two simulations are indicative of a rearrangement of the solvent shell which represents the major part of the overall reaaction barrier. Under these circumstances, the reactoin rate of an otherwise spontaneous reaction is limited by the intrinisic solvent relaxation time. This interpretation of the reactivity of hydrated radical cations reconciles previously confilicing experimental condensed phase and theoretical gas phase studies.
机译：用Car-Parrinello分子动力学模拟研究了乙烯自由基阳离子在水溶液中的溶剂化和反应。所有的从头算起的模拟都是使用56个水和一个乙烯分子的系统进行的。使用有利的乙烯分子。使用良好的对称溶剂自由基阳离子作为模拟的起点，可以观察到快速向自由基阳离子中添加水（在90 fs之内）。将主要的加成产物快速质子化（在100 fs内）以产生乙醇-2-基自由基。通过中性水合乙烯的垂直电离开始第二次模拟，这表示添加过程明显不利。在第二个模拟过程中，在1.7 ps的时间间隔内未观察到水的添加。两种模拟一起表明溶剂壳的重排，其代表整个反应障碍的主要部分。在这些情况下，本能溶剂的弛豫时间限制了其他自发反应的反应速率。对水合自由基阳离子反应性的这种解释使先前的实验冷凝相和理论气相研究相一致。

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