Thompson Ward H
Department of Chemistry, University of Kansas, Lawrence, Kansas 66045, USA.
J Phys Chem B. 2005 Sep 29;109(38):18201-8. doi: 10.1021/jp053043g.
The reaction dynamics for a model phenol-amine proton transfer system in a confined methyl chloride solvent have been simulated by mixed quantum-classical molecular dynamics. In this approach, the proton vibration is treated quantum mechanically (and adiabatically), while the rest of the system is described classically. Nonequilibrium trajectories are used to determine the proton transfer reaction rate constant. The reaction complex and methyl chloride solvent are confined in a smooth, hydrophobic spherical cavity, and radii of 10, 12, and 15 A have been considered. The effects of the cavity radius and the heavy atom (hydrogen bond) distance on the reaction dynamics are considered, and the mechanism of the proton transfer is examined in detail by analysis of the trajectories.
采用混合量子经典分子动力学方法模拟了在受限氯甲烷溶剂中一个模型苯酚 - 胺质子转移体系的反应动力学。在这种方法中，质子振动采用量子力学（且绝热）处理，而体系的其余部分采用经典描述。非平衡轨迹用于确定质子转移反应速率常数。反应复合物和氯甲烷溶剂被限制在一个光滑的疏水性球形腔内，考虑了半径为10埃、12埃和15埃的情况。考虑了腔半径和重原子（氢键）距离对反应动力学的影响，并通过轨迹分析详细研究了质子转移的机制。
