Solvent nuclear quantum effects in electron transfer reactions. III. Metal ions in water. Solute size and ligand effects
Solvent nuclear quantum effects in electron transfer reactions. III. Metal ions in water. Solute size and ligand effects
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DOI：
10.1063/1.1369128
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发表时间：
2001-06-01
影响因子：
4.4
通讯作者：
Ando, K
中科院分区：
文献类型：
--
作者：
Ando, K
通过分子动力学模拟分析，研究了水溶液中金属离子氧化还原电子转移反应中的溶剂核量子效应。通过与我们之前在一个中等大小的供体-受体系统中假设典型的有机荧光剂-猝灭剂分子的研究比较，研究了溶质大小和电荷变化以及溶剂配体效应的影响。化学。物理学报，106,116(1997)]。结果表明，溶剂与ET耦合的谱密度函数，以及量子ET速率及其能隙定律，强烈依赖于这些系统参数的变化。提出了两种分解分析，一种是来自内外球溶剂化的空间贡献，另一种是来自溶剂分子内振动和分子间集体模式的运动频率贡献。(C) 2001年美国物理研究所。
Solvent nuclear quantum effects in redox electron transfer (ET) reactions between metal ions in aqueous solution are studied via a molecular dynamics simulation analysis. The impacts of the solute size and charge variations together with the solvent ligand effects are examined by comparing with our previous study on a moderate size donor-acceptor system that assumed typical organic fluorescer-quencher molecules [J. Chem. Phys. 106, 116 (1997)]. It is shown that the spectral density function of the solvent coupling to ET, and consequently the quantum ET rate and its energy gap law, are strongly dependent on these variations of the system parameters. Two kinds of decomposition analysis, one into spatial contributions from inner- and outer-sphere solvations, and the other into motional frequency contributions from solvent intramolecular vibrations and intermolecular collective modes, are presented. (C) 2001 American Institute of Physics.