Herbert John M, Coons Marc P
Department of Chemistry and Biochemistry, The Ohio State University, Columbus, Ohio 43210; email:
Annu Rev Phys Chem. 2017 May 5;68:447-472. doi: 10.1146/annurev-physchem-052516-050816. Epub 2017 Mar 27.
Existence of a hydrated electron as a byproduct of water radiolysis was established more than 50 years ago, yet this species continues to attract significant attention due to its role in radiation chemistry, including DNA damage, and because questions persist regarding its detailed structure. This work provides an overview of what is known in regards to the structure and spectroscopy of the hydrated electron, both in liquid water and in clusters [Formula: see text], the latter of which provide model systems for how water networks accommodate an excess electron. In clusters, the existence of both surface-bound and internally bound states of the excess electron has elicited much debate, whereas in bulk water there are questions regarding how best to understand the structure of the excess electron's spin density. The energetics of the equilibrium species e(aq) and its excited states, in bulk water and at the air/water interface, are also addressed.
五十多年前就已证实水合电子作为水辐射分解的副产物存在，但由于其在包括DNA损伤在内的辐射化学中的作用，以及关于其详细结构的问题仍然存在，该物种继续吸引着人们的极大关注。这项工作概述了关于水合电子在液态水和团簇[化学式：见正文]中的结构和光谱的已知情况，后者为水网络如何容纳多余电子提供了模型系统。在团簇中，多余电子的表面结合态和内部结合态的存在引发了很多争论，而在 bulk water（此处可能有误，推测是“液态水”“bulk water”）中，关于如何最好地理解多余电子的自旋密度结构存在问题。还讨论了液态水和空气/水界面处平衡物种e(aq)及其激发态的能量学。
