Hydrogen bonding and Raman, IR, and 2D-IR spectroscopy of dilute HOD in liquid D2O
Hydrogen bonding and Raman, IR, and 2D-IR spectroscopy of dilute HOD in liquid D2O
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DOI：
10.1073/pnas.0701482104
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发表时间：
2007-09-04
影响因子：
11.1
通讯作者：
Skinner, J. L.
中科院分区：
文献类型：
--
作者：
Auer, B.;Kumar, R.;Skinner, J. L.
我们提出了改进我们以前的方法来计算振动光谱观测的OH拉伸区域的稀释HOD在液体D2 O。采用SPC/E模拟模型，采用这些改进的方法计算了红外光谱和各向同性拉曼光谱，结果与实验符合良好。我们还计算了与三脉冲红外回波相关的观测量：峰值位移和二维红外光谱。前者的计算结果与实验的一致性比我们以前的计算结果有了改善，但理论与实验之间的差异仍然存在。使用我们提出的定义氢键在液态水中，我们分解的频率分布在OH拉伸区域的HOD分子与不同的本地氢键环境的子集合。这种分解使我们能够与水分子团簇的实验和计算联系起来，更普遍地理解液体中跃迁频率和局部结构之间的关系。
We present improvements on our previous approaches for calculating vibrational spectroscopy observables for the OH stretch region of dilute HOD in liquid D2O. These revised approaches are implemented to calculate IR and isotropic Raman spectra, using the SPC/E simulation model, and the results are in good agreement with experiment. We also calculate observables associated with three-pulse IR echoes: the peak shift and 2D-IR spectrum. The agreement with experiment for the former is improved over our previous calculations, but discrepancies between theory and experiment still exist. Using our proposed definition for hydrogen bonding in liquid water, we decompose the distribution of frequencies in the OH stretch region in terms of subensembles of HOD molecules with different local hydrogen-bonding environments. Such a decomposition allows us to make the connection with experiments and calculations on water clusters and more generally to understand the extent of the relationship between transition frequency and local structure in the liquid.