Département de Chimie, Ecole Normale Supérieure, UMR CNRS-ENS-UPMC, Paris, France.
J Chem Phys. 2011 Feb 28;134(8):084302. doi: 10.1063/1.3533229.
We perform infrared vibrational analysis on small protonated water clusters H(+)(H(2)O)(n), with n = 2, [ellipsis (horizontal)], 6, at room temperature. The absorption spectra are calculated based on classical trajectories obtained by the multistate empirical valence bond method. The analysis is carried out based on the effective modes analysis, which has been recently developed [Martinez et al., J. Chem. Phys. 125, 144106 (2006)] as generalization of the normal modes analysis. This technique enables us to decompose the full spectrum in maximally localized bands which are obtained by accounting for temperature and anharmonic effects. These effects are especially considered in the determination of the modes coupling. The spectra of the small clusters are interpreted by identifying the behavior of the excess charge, by understanding the role of hydrogen bonds, and by considering the effect of (micro-)solvation. Our results are presented by showing comparisons with other numerical methods and experimental measurements which are available in the literature.
我们对室温下质子化的小水分子簇 H(+)(H(2)O)(n)（n = 2，[省略号]，6）进行了红外振动分析。吸收光谱是基于多态经验价键方法得到的经典轨迹计算得到的。分析是基于有效模式分析进行的，该方法是最近发展起来的[Martinez 等人，J. Chem. Phys. 125, 144106 (2006)]，是对简正模式分析的推广。该技术使我们能够通过考虑温度和非谐效应，将全谱分解为最大局域化的谱带。在确定模式耦合时特别考虑了这些效应。通过识别过剩电荷的行为、理解氢键的作用以及考虑（微观）溶剂化的影响，对小簇的光谱进行了解释。我们的结果通过与文献中可用的其他数值方法和实验测量进行比较来呈现。
