Intramolecular vibrational coupling in water molecules revealed by compatible multiple nonlinear vibrational spectroscopic measurements.
Intramolecular vibrational coupling in water molecules revealed by compatible multiple nonlinear vibrational spectroscopic measurements.
复制标题
DOI：
10.1039/c2an35684h
复制
发表时间：
2012-10
期刊：
影响因子：
--
通讯作者：
Shuji Ye;Sulan Ma;Feng Wei;Hongchun Li
中科院分区：
文献类型：
--
作者：
Shuji Ye;Sulan Ma;Feng Wei;Hongchun Li
水的复杂结构及其与固体表面的相互作用需要开发多种振动光谱测量来研究界面水和固体表面附近的本体水的分子结构。在这项研究中，新开发的兼容多重非线性振动光谱系统已用于研究离子固体（CaF（2）基质）和本体同位素D（2）O-HOD-H（2）O混合物界面区域中的水分子结构。使用该兼容系统，可以在相同的实验几何结构下收集相同水分子的和频发生（SFG）振动光谱和红外-红外-可见三泵场四波混合（IIV-TPF-FWM）光谱。研究发现，SFG 和 IIV-TPF-FWM 分别可用于表征界面距离低于 42 nm 的界面水和本体水分子的分子结构。 SFG 和 IIV-TPF-FWM 结果均表明分子内振动耦合在光谱中占主导地位。该方法获得的结果有助于阐明界面水以及固体表面附近的本体水振动耦合的起源。
The complex structure of water and its interactions with solid surfaces require the development of multiple vibrational spectroscopic measurements to study the molecular structure of interfacial water and bulk water near the solid surface. In this study, a newly developed compatible multiple nonlinear vibrational spectroscopy system has been applied to investigate the molecular structure of water in the interfacial region of an ionic solid (CaF(2) substrate) and bulk isotopic D(2)O-HOD-H(2)O mixtures. Using this compatible system, the sum frequency generation (SFG) vibrational spectra and infrared-infrared-visible three-pump-field four-wave-mixing (IIV-TPF-FWM) spectra of the same water molecules can be collected at the same experimental geometry. It is found that SFG and IIV-TPF-FWM can be used to characterize the molecular structures of interfacial water and bulk water molecules at an interfacial distance below 42 nm, respectively. SFG and IIV-TPF-FWM results both suggest an intramolecular vibrational coupling dominates the spectra. The results achieved by this method are helpful to clarify the origination of the vibrational coupling of the interfacial water as well as the bulk water near the solid surface.