Dynamics of water probed with vibrational echo correlation spectroscopy
Dynamics of water probed with vibrational echo correlation spectroscopy
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DOI：
10.1063/1.1818107
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发表时间：
2004-12-22
影响因子：
4.4
通讯作者：
Fayer, MD
中科院分区：
文献类型：
--
作者：
Asbury, JB;Steinel, T;Fayer, MD
利用振动回波相关光谱技术对水溶液中稀态HOD的OD伸缩进行了研究。一种方法被证明用于结合相关光谱与不同的红外脉冲带宽（脉冲持续时间），使人们有可能使用从许多实验中收集的数据，其中的激光脉冲特性是不相同的。精确测量的OD拉伸非谐性（162厘米（-1）），并用于数据分析。此外，最近精确测定的OD振动寿命（1.45 ps）和振动弛豫诱导断裂氢键“光产物”的时间尺度（类似于2 ps）有助于数据分析。利用含时图解微扰理论对数据进行分析，得到频率时间相关函数（FTCF）。结果是一个改进的FTCF相比，以前得到的振动回波相关光谱。实验数据和实验确定的FTCF进行比较，采用极化水模型（SPC-FQ）计算的FTCF。SPC-FQ推导的FTCF比以前测试的非极化水模型更接近实验结果，也被提出用于比较。(C)2004年，美国物理学会。
Vibrational echo correlation spectroscopy experiments on the OD stretch of dilute HOD in H2O are used to probe the structural dynamics of water. A method is demonstrated for combining correlation spectra taken with different infrared pulse bandwidths (pulse durations), making it possible to use data collected from many experiments in which the laser pulse properties are not identical. Accurate measurements of the OD stretch anharmonicity (162 cm(-1)) are presented and used in the data analysis. In addition, the recent accurate determination of the OD vibrational lifetime (1.45 ps) and the time scale for the production of vibrational relaxation induced broken hydrogen bond "photoproducts" (similar to2 ps) aid in the data analysis. The data are analyzed using time dependent diagrammatic perturbation theory to obtain the frequency time correlation function (FTCF). The results are an improved FTCF compared to that obtained previously with vibrational echo correlation spectroscopy. The experimental data and the experimentally determined FTCF are compared to calculations that employ a polarizable water model (SPC-FQ) to calculate the FTCF. The SPC-FQ derived FTCF is much closer to the experimental results than previously tested nonpolarizable water models which are also presented for comparison. (C) 2004 American Institute of Physics.