Insights into the dynamics of evaporation and proton migration in protonated water clusters from Large‐scale Born–Oppenheimer direct dynamics
Insights into the dynamics of evaporation and proton migration in protonated water clusters from Large‐scale Born–Oppenheimer direct dynamics
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DOI：
10.1002/jcc.23162
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发表时间：
2013-03
影响因子：
3
通讯作者：
V. Rybkin;A. Simakov;V. Bakken;Simen Reine;T. Kjærgaard;T. Helgaker;E. Uggerud
中科院分区：
文献类型：
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作者：
V. Rybkin;A. Simakov;V. Bakken;Simen Reine;T. Kjærgaard;T. Helgaker;E. Uggerud
利用最新的线性标度电子结构理论和轨道积分技术，对n=20和21的魔数(H2O)NH+周围的质子化水团簇进行了大规模的动态Born-Oppenheimer分子动力学模拟。除了证明计算方法的可行性和效率外，计算还揭示了有趣的动力学细节。研究发现，对于两种团簇大小，水分子的消除速度都很快，但对初始几何形状不敏感。释放的水分子获得与热能相容的速度。质子溶剂化壳层在众所周知的本征和Zundel基元之间变化，并以特定的低频振动模式为特征，这些模式已经被量化。质子转移机制与散装水很相似，但观察到一个有趣的变化。©2012 Wiley期刊，Inc.
Large‐scale on‐the‐fly Born–Oppenheimer molecular dynamics simulations using recent advances in linear scaling electronic structure theory and trajectory integration techniques have been performed for protonated water clusters around the magic number (H2O)nH+, for n = 20 and 21. Besides demonstrating the feasibility and efficiency of the computational approach, the calculations reveal interesting dynamical details. Elimination of water molecules is found to be fast for both cluster sizes but rather insensitive to the initial geometry. The water molecules released acquire velocities compatible with thermal energies. The proton solvation shell changes between the well‐known Eigen and Zundel motifs and is characterized by specific low‐frequency vibrational modes, which have been quantified. The proton transfer mechanism largely resembles that of bulk water but one interesting variation was observed. © 2012 Wiley Periodicals, Inc.