HO -（aq）的水合和流动性
Hydration and mobility of HO-(aq)
摘要：
氢氧根阴离子在许多化学和生物化学反应中起着重要作用。但是，目前对它的水合状态及其在水中的运输的分子尺度描述是有争议的。溶液的统计力学准化学理论表明，HO[H2O]3-是在标准条件下的水相的主要物种。这一结果与最近的氢氧化物水簇的光谱研究，并与可用的热力学水合自由能密切一致。而最近的从头计算分子动力学模拟表明，HO[H_2O]4-是水溶液中唯一的优势物种.我们应用绝热从头算分子动力学模拟，并找到良好的协议与准化学理论预测和实验结果。目前的结果表明，图片是更简单，更传统，但与额外的微妙。这些配位结构是不稳定的，但三配位物种是突出的情况。这一结论是不变的电子密度泛函的变化。没有证据表明HO[H2O]4-陷阱结构与HO[H2O]3-的速率决定性活化相互转化，介导氢氧化物的运输。HO-扩散作为质子空穴的跳跃的观点具有实质性的有效性，其速率在很大程度上取决于水氢键网络的动态无序。
英文摘要：
The hydroxide anion plays an essential role in many chemical and biochemical reactions. But a molecular-scale description of its hydration state, and hence also its transport, in water is currently controversial. The statistical mechanical quasi-chemical theory of solutions suggests that HO[H2O]3- is the predominant species in the aqueous phase under standard conditions. This result is in close agreement with recent spectroscopic studies on hydroxide water clusters, and with the available thermodynamic hydration free energies. In contrast, a recent ab initio molecular dynamics simulation has suggested that HO[H_2O]4- is the only dominant aqueous solution species. We apply adiabatic ab initio molecular dynamics simulations, and find good agreement with both the quasi-chemical theoretical predictions and experimental results. The present results suggest a picture that is simpler, more traditional, but with additional subtlety. These coordination structures are labile but the tri-coordinate species is the prominent case. This conclusion is unaltered with changes in the electronic density functional. No evidence is found for rate-determining activated inter-conversion of a HO[H2O]4- trap structure to HO[H2O]3-, mediating hydroxide transport. The view of HO- diffusion as the hopping of a proton hole has substantial validity, the rate depending largely on the dynamic disorder of the water hydrogen-bond network.
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