Department of Chemistry, The Ohio State University, Columbus, Ohio 43210, United States.
J Phys Chem A. 2011 Dec 22;115(50):14470-83. doi: 10.1021/jp206391d. Epub 2011 Nov 22.
The prevailing structural paradigm for the aqueous electron is that of an s-like ground-state wave function that inhabits a quasi-spherical solvent cavity, a viewpoint that is supported by numerous atomistic simulations using various one-electron pseudopotential models. This conceptual picture has recently been challenged, however, on the basis of results obtained from a new electron-water pseudopotential model that predicts a more delocalized wave function and no well-defined solvent cavity. Here, we examine this new model in comparison to two alternative, cavity-forming pseudopotential models. We find that the cavity-forming models are far more consistent with the experimental data for the electron's radius of gyration, optical absorption spectrum, and vertical electron binding energy. Calculations of the absorption spectrum using time-dependent density functional theory are in quantitative or semiquantitative agreement with experiment when the solvent geometries are obtained from the cavity-forming pseudopotential models, but differ markedly from experiment when geometries that do not form a cavity are used.
水合电子的主要结构范式是一种类似 s 波的基态波函数，占据一个拟球型溶剂空腔，这一观点得到了大量使用各种单电子赝势模型的原子模拟的支持。然而，最近基于新的电子-水赝势模型的结果对这一概念模型提出了挑战，该模型预测了一个更离域的波函数和没有明确界定的溶剂空腔。在这里，我们将这个新模型与两个替代的、形成空腔的赝势模型进行了比较。我们发现，对于电子的转动半径、光吸收光谱和垂直电子结合能，形成空腔的模型与实验数据更为一致。当溶剂几何形状从形成空腔的赝势模型中获得时，使用含时密度泛函理论计算的吸收光谱与实验定量或半定量吻合，但当使用不形成空腔的几何形状时，与实验有明显差异。
