Department of Chemistry, Northwestern University, Evanston, IL 60208, USA.
Phys Chem Chem Phys. 2012 Jan 14;14(2):405-14. doi: 10.1039/c1cp22767j. Epub 2011 Nov 28.
Mapping out multidimensional potential energy surfaces has been a goal of physical chemistry for decades in the quest to both predict and control chemical reactivity. Recently a new spectroscopic approach called Femtosecond Stimulated Raman Spectroscopy or FSRS was introduced that can structurally interrogate multiple dimensions of a reactive potential energy surface. FSRS is an ultrafast laser technique which provides complete time-resolved, background-free Raman spectra in a few laser shots. The FSRS technique provides simultaneous ultrafast time (50 fs) and spectral (8 cm(-1)) resolution, thus enabling one to follow reactive structural evolutions as they occur. In this perspective we summarize how FSRS has been used to follow structural dynamics and provide mechanistic detail on three classical chemical reactions: a structural isomerization, an electron transfer reaction, and a proton transfer reaction.
绘制多维势能面一直是物理化学几十年来的目标，旨在预测和控制化学反应性。最近引入了一种称为飞秒受激拉曼光谱学（FSRS）的新光谱方法，该方法可以对反应势能面的多个维度进行结构探测。FSRS 是一种超快激光技术，可在几次激光射击中提供完整的、无背景的时间分辨拉曼光谱。FSRS 技术提供了同时的超快时间（50 fs）和光谱（8 cm(-1)）分辨率，从而能够在反应发生时跟踪反应结构的演变。在这篇观点文章中，我们总结了 FSRS 如何用于跟踪结构动力学，并提供三个经典化学反应的机制细节：结构异构化、电子转移反应和质子转移反应。
