Vibrational spectroscopy of water at interfaces.
Vibrational spectroscopy of water at interfaces.
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DOI：
10.1021/ar200122a
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发表时间：
2012-01-17
影响因子：
18.3
通讯作者：
Gruenbaum, S. M.
中科院分区：
文献类型：
--
作者：
Skinner, J. L.;Pieniazek, P. A.;Gruenbaum, S. M.
振动光谱学的最新实验进展，如超快脉冲和外差探测，使得以前所未有的细节探测体水和界面水的结构和动力学成为可能。我们考虑了三种水界面：水-液/气界面，水与反胶束表面活性基团的界面，水与排列的多层膜的脂头基团的界面。在第一种情况下，使用和频谱探测界面，而在第二种和第三种情况下，承压水池足够小，可以使用FTIR、泵浦-探测、2DIR等体谱技术来探测界面水。在这篇综述中，我们讨论了我们试图对这三个系统进行建模的尝试，并解释了现有的实验。特别是，对于水-液/气界面，我们发现三体相互作用对于再现实验和频谱是必不可少的，并且可能对界面的结构也是必要的。观察到的光谱被解释为重叠和抵消了不同氢键环境中分子的正负贡献。对于反胶束，我们的理论模型证实了实验观察到的水OD伸展的蓝移(对于H2O中的稀HOD)是由于较弱的氢键与磺酸氧的作用。我们将水旋转动力学中观察到的减速解释为曲率诱导的受挫。对于限制在脂质双层之间的水，我们的理论模型证实了实验观察到的水的外径伸展的红移是由于更强的氢键与磷酸根形成的。我们建立了一个非均匀振动寿命分布模型，并用该模型计算了各向同性和各向异性的泵浦-探测衰变，并与实验进行了比较。
Recent experimental advances in vibrational spectroscopy, such as ultrafast pulses and heterodyne detection, have made it possible to probe the structure and dynamics of bulk and interfacial water in unprecedented detail. We consider three aqueous interfaces: the water liquid/vapor interface, the interface between water and the surfactant headgroups of reverse micelles, and the interface between water and the lipid headgroups of aligned multi-bilayers. In the first case, sum-frequency spectroscopy is used to probe the interface, while in the second and third cases, the confined water pools are sufficiently small that techniques of bulk spectroscopy such as FTIR, pump-probe, 2DIR, etc. can be used to probe the interfacial water. In this review, we discuss our attempts to model these three systems and interpret the existing experiments. In particular, for the water liquid/vapor interface we find that three-body interactions are essential for reproducing the experimental sum-frequency spectrum, and presumably for the structure of the interface as well. The observed spectrum is interpreted as arising from overlapping and cancelling positive and negative contributions from molecules in different hydrogen-bonding environments. For the reverse micelles, our theoretical models confirm that the experimentally observed blue shift of the water OD stretch (for dilute HOD in H2O) arises from weaker hydrogen bonding to sulfonate oxygens. We interpret the observed slow-down in water rotational dynamics as arising from curvature-induced frustration. For the water confined between lipid bilayers, our theoretical models confirm that the experimentally observed red shift of the water OD stretch arises from stronger hydrogen bonding to phosphate oxygens. We develop a model for heterogeneous vibrational lifetime distributions, and implement the model to calculate isotropic and anisotropic pump-probe decays, and compare with experiment.
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DOI：
10.1021/jp902004r
发表时间：
2009-06-25
期刊：
The journal of physical chemistry. B
影响因子：
--
作者：
Moilanen DE;Fenn EE;Wong D;Fayer MD
通讯作者：
Fayer MD
影响因子：
3.3
作者：
Cringus, Dan;Bakulin, Artem;Wiersma, Douwe A.
通讯作者：
Wiersma, Douwe A.
影响因子：
4.4
作者：
Dokter, Adriaan M.;Woutersen, Sander;Bakker, Huib J.
通讯作者：
Bakker, Huib J.
影响因子：
4.4
作者：
Jansen, T. L. C.;Auer, B. M.;Skinner, J. L.
通讯作者：
Skinner, J. L.
影响因子：
4.4
作者：
JORGENSEN, WL;CHANDRASEKHAR, J;KLEIN, ML
通讯作者：
KLEIN, ML