Simmons Philip D, Turley Hubert K, Silverstein Daniel W, Jensen Lasse, Camden Jon P
Department of Chemistry, University of Tennessee , Knoxville, Tennessee 37996, United States.
Department of Chemistry and Biochemistry, University of Notre Dame , Notre Dame, Indiana 46556, United States.
J Phys Chem Lett. 2015 Dec 17;6(24):5067-71. doi: 10.1021/acs.jpclett.5b02342. Epub 2015 Dec 8.
Motivated to explore the ultimate limits of surface-enhanced nonlinear spectroscopies, we report on the first observation of molecular second hyper-Raman scattering with the aid of surface enhancement and provide a new theoretical framework for first-principles calculations of the second hyper-Raman effect. Second hyper-Raman enhancement factors, determined to be a minimum of 10(5) times stronger than those in Raman scattering, demonstrate a clear trend toward larger enhancements for nonlinear phenomena, and the nearly quantitative agreement between simulation and experiment provides a unique spectroscopic window into higher-order molecular responses.
受探索表面增强非线性光谱极限的驱动，我们报告了借助表面增强首次观测到分子二次超拉曼散射，并为二次超拉曼效应的第一性原理计算提供了新的理论框架。二次超拉曼增强因子被确定至少比拉曼散射中的增强因子强10^5倍，这表明非线性现象有明显的增强趋势，模拟与实验之间几乎定量的一致性为高阶分子响应提供了一个独特的光谱窗口。
