Department of Chemistry, The Ohio State University, Columbus, Ohio 43210, USA.
J Am Chem Soc. 2010 Jul 28;132(29):10000-2. doi: 10.1021/ja1042484.
The electronic absorption spectrum of the aqueous electron in bulk water has been simulated using long-range-corrected time-dependent density functional theory as well as mixed quantum/classical molecular dynamics based on a one-electron model in which electron-water polarization is treated self-consistently. Both methodologies suggest that the high-energy Lorentzian tail that is observed experimentally arises mostly from delocalized bound-state excitations of the electron rather than bound-to-continuum excitations, as is usually assumed. Excited states in the blue tail are bound only by polarization of the solvent electron density. These findings have potentially important ramifications for understanding electron localization in polar condensed media as well as biological radiation damage arising from dissociative electron attachment.
使用长程修正的含时密度泛函理论以及基于单电子模型的混合量子/经典分子动力学，对体相水中电子的电子吸收光谱进行了模拟，其中电子-水极化作用是自洽处理的。这两种方法都表明，实验中观察到的高能洛伦兹ian 尾部主要来自电子的离域束缚态激发，而不是通常假设的束缚态到连续态的激发。蓝尾中的激发态仅通过溶剂电子密度的极化而束缚。这些发现对于理解极性凝聚介质中的电子局域化以及源于离域电子俘获的生物辐射损伤具有潜在的重要意义。
