The Electron Attachment Energy of the Aqueous Hydroxyl Radical Predicted from the Detachment Energy of the Aqueous Hydroxide Anion

被引:46
作者
Adriaanse, Christopher [1 ]
Sulpizi, Marialore [1 ]
VandeVondele, Joost [2 ]
Sprik, Michiel [1 ]
机构
[1] Univ Cambridge, Dept Chem, Cambridge CB2 1EW, England
[2] Univ Zurich, Inst Phys Chem, CH-8057 Zurich, Switzerland
基金
英国工程与自然科学研究理事会;
关键词
DENSITY-FUNCTIONAL THEORY; MOLECULAR-DYNAMICS; LIQUID WATER; SPECTROSCOPY; CLUSTER; OH;
D O I
10.1021/ja809155k
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
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.
引用
收藏
页码:6046 / +
页数:3
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