Dynamical effects on vibrational and electronic spectra of hydroperoxyl radical water clusters
Dynamical effects on vibrational and electronic spectra of hydroperoxyl radical water clusters
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DOI：
10.1063/1.2006674
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发表时间：
2005-08-22
影响因子：
4.4
通讯作者：
Iyengar, SS
中科院分区：
文献类型：
--
作者：
Iyengar, SS
我们对过氧化氢水团簇进行了从头算分子动力学研究。我们的研究得到了优化，频率和激发态计算的补充。我们得到的三个主要结果是：（a）在过氧化氢水分子团簇体系中，最高占据分子轨道和最低未占据分子轨道之间的动态平均能隙随水分子数目的增加而单调减小;（B）有限温度下势能面的动态平均化使电子激发光谱变宽，红外光谱发生非平凡的变化，（c）动力学模拟的结构分析表明，溶剂化的过氧化氢-水团簇中的氧-氧距离与质子化的水团簇（Zundel：H_5O ~（2+））中的氧-氧距离非常相似，尽管后者带正电荷而过氧化氢-水团簇不带正电荷。动力学电荷分析和HO 2的弱酸性被用来证明这一结果。(c)2005年美国物理学会。
We have carried out ab initio molecular-dynamics studies on hydroperoxyl water clusters. Our studies are complemented by optimization, frequency, and excited-state calculations. The three main results we obtained are (a) the dynamically averaged energy gap between the highest-occupied molecular orbital and the lowest-unoccupied molecular orbital monotonically decreases as the number of water molecules is increased in a hydroperoxyl water cluster system, (b) the dynamical averaging of the potential-energy surface at finite temperature broadens the electronic excitation spectrum and changes the infrared spectrum in nontrivial ways, and (c) the structural analysis of our dynamics simulation indicates that the oxygen-oxygen distance in a solvated hydroperoxyl-water cluster is very similar to that found in protonated water clusters (Zundel: H5O2+) inspite of the fact that the latter possesses a positive charge and the hydroperoxyl-water cluster does not. Dynamical charge analysis and the weak acidity of HO2 are used to justify this result. (c) 2005 American Institute of Physics.