Analysis of anisotropic local field in sum frequency generation spectroscopy with the charge response kernel water model
Analysis of anisotropic local field in sum frequency generation spectroscopy with the charge response kernel water model
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DOI：
10.1063/1.3279126
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发表时间：
2009-12-28
影响因子：
4.4
通讯作者：
Morita, Akihiro
中科院分区：
文献类型：
--
作者：
Ishiyama, Tatsuya;Morita, Akihiro
提出了一种基于电荷响应核（CRK）理论的柔性极化水模型，用于和频产生（SFG）光谱分析。通过分子动力学（MD）计算，CRK模型很好地描述了几种体水性质和SFG谱。柔性极化分子动力学模拟一般采用分子间相互作用的短程阻尼，但对于强氢键环境下跃迁偶极子的计算，这种方法并不适用。因此，改进后的水面非线性磁化率计算结果在3000 ~ 3200cm（-1）区域为正虚部，这与最近的相敏实验结果一致。正区形成的机制是由地表水的取向相关性引起的各向异性局域场效应引起的。
A new flexible and polarizable water model based on the charge response kernel (CRK) theory is developed for the analysis of sum frequency generation (SFG) spectroscopy. The CRK model well describes several bulk water properties and SFG spectrum by molecular dynamics (MD) calculations. While the flexible and polarizable MD simulation generally adopts the short-range damping of intermolecular interaction, it is found that the same procedure is not adequate for the calculation of transition dipole in strongly hydrogen bonding environment. Accordingly, the improved calculation of the nonlinear susceptibility of water surface results in the positive imaginary part in the 3000-3200 cm(-1) region, which is consistent with recent phase-sensitive experiments. The mechanism of the positive region is attributed to the anisotropic local field effect induced by the orientational correlation of surface water.