Vibrational spectroscopy of HOD in liquid D2O.: VII.: Temperature and frequency dependence of the OH stretch lifetime
Vibrational spectroscopy of HOD in liquid D2O.: VII.: Temperature and frequency dependence of the OH stretch lifetime
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DOI：
10.1063/1.1591178
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发表时间：
2003-08-15
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
最近的实验表明，在液态D_2O中，稀态HOD的OH伸缩振动基频的振动寿命与温度和激发频率有着迷人的依赖关系。特别地，寿命随着温度的增加而增加，并且随着激发频率的增加而增加。使用我们以前开发的这个系统中的振动弛豫的理论模型，我们计算了寿命的温度和频率依赖性，再现了所观察到的实验趋势。这两种效应的物理起源是相似的，并且涉及OH基波和（HOD的）弯曲泛音之间的能隙对温度和频率的依赖性。我们的模型在描述实验中的成功提供了一些支持的松弛机制，它意味着，这主要涉及直接激发的弯曲泛音。(C)2003年，美国物理学会。
Recent experiments have shown that the vibrational lifetime of the OH stretch fundamental of dilute HOD in liquid D2O has fascinating dependences on temperature and excitation frequency. In particular, the lifetime increases with increasing temperature and increases with increasing excitation frequency. Using the theoretical model for vibrational relaxation in this system that we developed previously, we calculate the temperature and frequency dependence of the lifetime, reproducing the observed experimental trends. The physical origins of both effects are similar, and involve the dependence of the energy gap between the OH fundamental and the bend overtone (of HOD) on temperature and frequency. The success of our model in describing the experiments provides some support for the relaxation mechanism it implies, which primarily involves direct excitation of the bend overtone. (C) 2003 American Institute of Physics.