Lynch Pauline G, Das Aritra, Alam Shahzad, Rich Christopher C, Frontiera Renee R
Department of Chemistry, University of Minnesota, Minneapolis, Minnesota 55455, United States.
ACS Phys Chem Au. 2023 Oct 21;4(1):1-18. doi: 10.1021/acsphyschemau.3c00031. eCollection 2024 Jan 24.
Femtosecond stimulated Raman spectroscopy (FSRS) is a powerful nonlinear spectroscopic technique that probes changes in molecular and material structure with high temporal and spectral resolution. With proper spectral interpretation, this is equivalent to mapping out reactive pathways on highly anharmonic excited-state potential energy surfaces with femtosecond to picosecond time resolution. FSRS has been used to examine structural dynamics in a wide range of samples, including photoactive proteins, photovoltaic materials, plasmonic nanostructures, polymers, and a range of others, with experiments performed in multiple groups around the world. As the FSRS technique grows in popularity and is increasingly implemented in user facilities, there is a need for a widespread understanding of the methodology and best practices. In this review, we present a practical guide to FSRS, including discussions of instrumentation, as well as data acquisition and analysis. First, we describe common methods of generating the three pulses required for FSRS: the probe, Raman pump, and actinic pump, including a discussion of the parameters to consider when selecting a beam generation method. We then outline approaches for effective and efficient FSRS data acquisition. We discuss common data analysis techniques for FSRS, as well as more advanced analyses aimed at extracting small signals on a large background. We conclude with a discussion of some of the new directions for FSRS research, including spectromicroscopy. Overall, this review provides researchers with a practical handbook for FSRS as a technique with the aim of encouraging many scientists and engineers to use it in their research.
飞秒受激拉曼光谱（FSRS）是一种强大的非线性光谱技术，能够以高时间和光谱分辨率探测分子和材料结构的变化。通过适当的光谱解释，这相当于以飞秒到皮秒的时间分辨率在高度非谐的激发态势能面上绘制反应路径。FSRS已被用于研究各种样品中的结构动力学，包括光活性蛋白、光伏材料、等离子体纳米结构、聚合物等，世界各地的多个研究小组都开展了相关实验。随着FSRS技术越来越受欢迎并在用户设施中得到越来越广泛的应用，人们需要对其方法和最佳实践有广泛的了解。在这篇综述中，我们提供了一份FSRS实用指南，包括对仪器设备以及数据采集与分析的讨论。首先，我们描述产生FSRS所需的三个脉冲（探测脉冲、拉曼泵浦脉冲和光化泵浦脉冲）的常用方法，包括在选择光束产生方法时需要考虑的参数。然后，我们概述有效且高效的FSRS数据采集方法。我们讨论FSRS常用的数据分析技术，以及旨在在大背景下提取小信号的更高级分析方法。最后，我们讨论了FSRS研究的一些新方向，包括光谱显微镜技术。总的来说，这篇综述为研究人员提供了一本FSRS实用手册，旨在鼓励众多科学家和工程师在其研究中使用该技术。
