Vibrational spectroscopy of HOD in liquid D2O.: II.: Infrared line shapes and vibrational Stokes shift
Vibrational spectroscopy of HOD in liquid D2O.: II.: Infrared line shapes and vibrational Stokes shift
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DOI：
10.1063/1.1514652
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发表时间：
2002-11-15
影响因子：
4.4
通讯作者：
Skinner, JL
中科院分区：
文献类型：
--
作者：
Lawrence, CP;Skinner, JL
我们提出了液体 D2O 中稀释 HOD 的三种分子内振动的红外线形状的半经典计算。在这些计算中，HOD 的振动被量子力学处理，所有分子的旋转和平移都被经典处理。该方法和模型基于 Oxtoby 以及 Rey 和 Hynes 的早期工作，在本系列的论文 I（关于同一系统中的振动能量弛豫）中详细讨论了该方法和模型。我们方法的一个新颖特征是自洽重整化方案，用于确定 HOD 分子给定振动状态的系统和浴哈密顿量。我们的线形状结果与实验相当一致。我们还探讨了导致线形的频率波动在多大程度上呈高斯分布。最后，我们计算 OH 拉伸基波的振动斯托克斯位移。我们的结果是非零，只是因为浴哈密顿量的规范取决于 HOD 分子的振动状态（作为自洽重正化方案的结果），结果为 57 cm(-1)，与实验数 70 cm(-1) 非常一致。 (C) 2002 年美国物理研究所。
We present semiclassical calculations of the infrared line shapes for the three intramolecular vibrations of dilute HOD in liquid D2O. In these calculations the vibrations of HOD are treated quantum mechanically, and the rotations and translations of all the molecules are treated classically. The approach and model, which is based on earlier work of Oxtoby and of Rey and Hynes, was discussed in detail in Paper I, on vibrational energy relaxation in the same system, of this series. A novel feature of our approach is a self-consistent renormalization scheme for determining the system and bath Hamiltonians for a given vibrational state of the HOD molecule. Our results for the line shapes are in reasonable agreement with experiment. We also explore the extent to which the frequency fluctuations leading to the line shape are Gaussian. Finally, we calculate the vibrational Stokes shift for the OH stretch fundamental. Our result, which is nonzero only because the specification of the bath Hamiltonian depends on the vibrational state of the HOD molecule (as a result of the self-consistent renormalization scheme), is 57 cm(-1), in good agreement with the experimental number of 70 cm(-1). (C) 2002 American Institute of Physics.