Electron solvation by highly polar molecules: density functional theory study of atomic sodium interaction with water, ammonia, and methanol.
Electron solvation by highly polar molecules: density functional theory study of atomic sodium interaction with water, ammonia, and methanol.
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高极性分子的电子溶剂化：原子钠与水、氨和甲醇相互作用的密度泛函理论研究。
DOI：
10.1063/1.1690238
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发表时间：
2004
期刊：
影响因子：
--
通讯作者：
Volker Kempter
中科院分区：
文献类型：
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作者：
Y. Ferro;A. Allouche;Volker Kempter
这项研究进一步扩展了前一篇论文的范围[Y.Ferro和A.Alouche，J.Chem。太棒了。第118,10461(2003年)]关于原子钠与水的反应性到其他一些高极性分子的反应性，这些分子以与有效氢键相连的溶剂化性质而闻名。将氨和甲醇的溶剂化机理与水合机理进行了比较。结果表明，在氨的情况下，溶剂体系的稳定性仅由静电相互作用保证，而甲醇的作用更接近于水的作用。对3S价Na电子的溶剂化过程给予了更具体的关注。分析了对化学反应性的影响：氨与原子钠相互作用时是不反应的，而甲醇则有两个化学反应。第一个过程是脱氢，产生甲氧基物种和氢气。另一种是脱水，最终产物是甲氧基物种，但也有甲基自由基和水。从反应体系的态密度出发，详细分析了电子溶剂化和氢键网络的各自作用。
This study further extends the scope of a previous paper [Y. Ferro and A. Allouche, J. Chem. Phys. 118, 10461 (2003)] on the reactivity of atomic Na with water to some other highly polar molecules known for their solvation properties connected to efficient hydrogen bonding. The solvation mechanisms of ammonia and methanol are compared to the hydration mechanism. It is shown that in the case of ammonia, the stability of the solvated system is only ensured by electrostatic interactions, whereas the methanol action is more similar to that of water. More specific attention is given to the solvation process of the valence 3s Na electron. The consequences on the chemical reactivity are analyzed: Whereas ammonia is nonreactive when interacting with atomic sodium, two chemical reactions are proposed for methanol. The first process is dehydrogenation and yields methoxy species and hydrogen. The other one is dehydration and the final products are methoxy species, but also methyl radical and water. The respective roles of electron solvation and hydrogen bonds network are analyzed in detail in view of the density of states of the reactive systems.