THE JOURNAL OF PHYSICAL CHEMISTRY B
THE JOURNAL OF PHYSICAL CHEMISTRY B
复制标题
DOI：
10.1021/issn.1520-6106
复制
发表时间：
--
期刊：
影响因子：
--
通讯作者：
中科院分区：
文献类型：
--
作者：
当前位置水合电子是在液态水中加入一个多余的电子所产生的物质，它一直是人们感兴趣的焦点，这既是因为它在辐射化学和其他化学反应中的作用，也是因为它提供了一个看似简单的系统，可以作为一种手段来对抗量子分子动力学模拟的预测与实验。尽管如此，关于水合电子的分子结构仍然存在相当大的争论：它是否占据一个空腔，是否有大量的内部水分子，或者是否有介于两者之间的结构？所有这些争论的原因是，不同的计算机模拟产生了这些不同的结构中的每一种，然而这些不同结构的预测性质仍然与实验合理一致。在这篇专题文章中，我们探讨了在不同赝势用于水合电子的量子模拟时产生不同结构的原因。我们还表明，基本上所有水合电子的不同模型，包括完全从头计算的模型，电子的波函数与附近的水分子的直接重叠相对较少。因此，一个非空穴水合电子最好被看作是一个“反葡萄干布丁“模型，内部的沃茨局部地驱逐周围电子的电荷密度。最后，我们还探讨了不同的水合电子模型和某些关键实验之间的协议，如共振拉曼光谱和温度依赖性和光学吸收光谱的均匀加宽程度，以区分不同的模拟结构。综上所述，我们得出结论，水合电子可能有大量的内部
: The hydrated electron the species that results from the addition of a single excess electron to liquid water has been the focus of much interest both because of its role in radiation chemistry and other chemical reactions, and because it provides for a deceptively simple system that can serve as a means to confront the predictions of quantum molecular dynamics simulations with experiment. Despite all this interest, there is still considerable debate over the molecular structure of the hydrated electron: does it occupy a cavity, have a signi fi cant number of interior water molecules, or have a structure somewhere in between? The reason for all this debate is that di ff erent computer simulations have produced each of these di ff erent structures, yet the predicted properties for these di ff erent structures are still in reasonable agreement with experiment. In this Feature Article, we explore the reasons underlying why di ff erent structures are produced when di ff erent pseudopotentials are used in quantum simulations of the hydrated electron. We also show that essentially all the di ff erent models for the hydrated electron, including those from fully ab initio calculations, have relatively little direct overlap of the electron ’ s wave function with the nearby water molecules. Thus, a non-cavity hydrated electron is better thought of as an “ inverse plum pudding ” model, with interior waters that locally expel the surrounding electron ’ s charge density. Finally, we also explore the agreement between di ff erent hydrated electron models and certain key experiments, such as resonance Raman spectroscopy and the temperature dependence and degree of homogeneous broadening of the optical absorption spectrum, in order to distinguish between the di ff erent simulated structures. Taken together, we conclude that the hydrated electron likely has a signi fi cant number of interior