Department of Physics, University of Hamburg and Center for Free Electron Laser Science , 22761 Hamburg, Germany.
Max Planck Institute for the Structure and Dynamics of Matter , 22761 Hamburg, Germany.
J Am Chem Soc. 2017 Apr 5;139(13):4797-4804. doi: 10.1021/jacs.6b12992. Epub 2017 Mar 27.
We applied time-resolved sulfur-1s absorption spectroscopy to a model aromatic thiol system as a promising method for tracking chemical reactions in solution. Sulfur-1s absorption spectroscopy allows tracking multiple sulfur species with a time resolution of ∼70 ps at synchrotron radiation facilities. Experimental transient spectra combined with high-level electronic structure theory allow identification of a radical and two thione isomers, which are generated upon illumination with 267 nm radiation. Moreover, the regioselectivity of the thione isomerization is explained by the resulting radical frontier orbitals. This work demonstrates the usefulness and potential of time-resolved sulfur-1s absorption spectroscopy for tracking multiple chemical reaction pathways and transient products of sulfur-containing molecules in solution.
我们将时间分辨硫 1s 吸收光谱应用于模型芳香硫醇体系，作为跟踪溶液中化学反应的一种很有前途的方法。硫 1s 吸收光谱允许在同步辐射设施中以 ∼70 ps 的时间分辨率跟踪多种硫物种。实验瞬态光谱结合高水平的电子结构理论可以识别自由基和两种硫酮异构体，它们是在 267nm 辐射照射下产生的。此外，硫酮异构化的区域选择性可以通过生成的自由基前线轨道来解释。这项工作证明了时间分辨硫 1s 吸收光谱在跟踪溶液中含硫分子的多种化学反应途径和瞬态产物方面的有用性和潜力。
