The Electron Attachment Energy of the Aqueous Hydroxyl Radical Predicted from the Detachment Energy of the Aqueous Hydroxide Anion
The Electron Attachment Energy of the Aqueous Hydroxyl Radical Predicted from the Detachment Energy of the Aqueous Hydroxide Anion
复制标题
DOI：
10.1021/ja809155k
复制
发表时间：
2009-05-06
影响因子：
15
通讯作者：
Sprik, Michiel
中科院分区：
文献类型：
--
作者：
Adriaanse, Christopher;Sulpizi, Marialore;Sprik, Michiel
结合光电发射和电化学数据从文献中，我们认为，水溶液的氢氧阴离子的垂直和绝热电离能之间的差异是2.9 eV。然后，我们使用基于密度泛函理论的分子动力学表明，溶剂的电离响应是非线性的。将此添加到实验数据中，我们预测电子垂直附着到水羟基自由基的能量和相应的绝热电子亲和力之间的差异为4.1 eV。这使得接受电子的状态仅低于真空2.2 eV或高于水的价带边缘7.7 eV。
Combining photoemission and electrochemical data from the literature we argue that the difference between the vertical and adiabatic ionization energy of the aqueous hydroxide anion is 2.9 eV. We then use density functional theory based molecular dynamics to show that the solvent response to ionization is nonlinear. Adding this to the experimental data we predict a 4.1 eV difference between the energy for vertical attachment of an electron to the aqueous hydroxyl radical and the corresponding adiabatic electron affinity. This places the state accepting the electron only 2.2 eV below vacuum or 7.7 eV above the edge of the valence band of water.