电化学表面增强拉曼光谱的量子化学研究

摘要

Considering the study of electrochemical surface adsorption and reaction processes at the molecular level, Surface-enhanced Raman spectroscopy( SERS) shows its particular merits and provides a powerful tech-nical method for this study. However, the mechanism of enhancement needs to be further explored. This re-view summarizes the systematic work on electrochemical SERS ( EC-SERS ) by combining quantum chemistry calculations. On the basis of these studies, we can make deep insight for extracting the physical and chemical information in EC-SERS spectra. Focusing on adsorption of pyridine on the electrochemical surface, adsorption and reactional process of water on the surface, and surface coupling reaction for p-aminothiophenol, we had illustrated the nature of the adsorption and photochemical reactions on the electrochemical surface.%对于在分子水平上研究电化学表面吸附和反应过程，表面增强拉曼光谱( SERS)显示出了其独到的优势，提供了有力的技术方法，但对于其表面增强机理仍有待深入研究。本文总结了将量子化学计算应用于电化学表面增强拉曼光谱( EC-SERS)分析的研究，以电化学界面分子吸附、电化学反应以及光电化学反应的研究体系为模型，提取EC-SERS光谱所蕴藏的物理化学信息。通过对吡啶在电化学表面的吸附、水的吸附及其电化学反应、以及对巯基苯胺的电化学表面催化偶联反应等体系的研究，揭示了电化学表面吸附、反应和光电化学过程的本质。