Lee Han Myoung, Kim Dongwook, Singh N Jiten, Kołaski Maciej, Kim Kwang S
Department of Chemistry, Pohang University of Science and Technology, Pohang 790-784, Korea.
J Chem Phys. 2007 Oct 28;127(16):164311. doi: 10.1063/1.2778423.
On the basis of density functional theory (DFT) and high level ab initio theory, we report the structures, binding energies, thermodynamic quantities, IR spectra, and electronic properties of the hydride anion hydrated by up to six water molecules. Ground state DFT molecular dynamics simulations (based on the Born-Oppenheimer potential surface) show that as the temperature increases, the surface-bound hydride anion changes to the internally bound structure. Car-Parrinello molecular dynamics simulations are also carried out for the spectral analysis of the monohydrated hydride. Excited-state ab initio molecular dynamics simulations show that the photoinduced charge-transfer-to-solvent phenomena are accompanied by the formation of the excess electron-water clusters and the detachment of the H radical from the clusters. The dynamics of the detachment process of a hydrogen radical upon the excitation is discussed.
基于密度泛函理论（DFT）和高水平从头算理论，我们报道了由多达六个水分子水合的氢负离子的结构、结合能、热力学量、红外光谱和电子性质。基态DFT分子动力学模拟（基于玻恩-奥本海默势能面）表明，随着温度升高，表面结合的氢负离子转变为内部结合结构。还进行了Car-Parrinello分子动力学模拟以对一水合氢化物进行光谱分析。激发态从头算分子动力学模拟表明，光诱导的电荷转移到溶剂现象伴随着过量电子-水团簇的形成以及H自由基从团簇中的脱离。讨论了激发时氢自由基脱离过程的动力学。
