We report vibrationally resolved threshold photoelectron spectra of several sulfur-containing reactive intermediates. This includes the organosulfur radicals CH₂S, CH₃S, CH₂SH, CH₃S₂, and S₂H, which are relevant in atmospheric chemistry and in astrochemical settings. Due to the high reactivity, the radicals were prepared in situ via pyrolysis of (CH₃)₂S₂. The organosulfur species were characterized by photoion mass-selected threshold photoelectron spectroscopy, employing the photoelectron-photoion coincidence setup (PEPICO) and synchrotron radiation from the Swiss Light Source. We report improved ionization energies and characterize ionic ground and excited states, both singlet and triplet. The vibrational structure was simulated based on computed geometries and vibrational frequencies, giving insight into the geometry change upon ionization.

中文翻译：

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有机硫自由基的阈值光电子能谱


我们报道了几种含硫反应性中间体的振动分辨阈值光电子谱。这包括有机硫自由基 CH₂S、CH₃S、CH₂SH、CH₃S₂ 和 S₂H，它们与大气化学和天体化学环境有关。由于反应性高，通过 （CH₃）₂S₂ 的热解原位制备自由基。通过光离子质量选择的阈值光电子能谱对有机硫种类进行表征，采用光电-光离子符合装置 （PEPICO） 和来自瑞士光源的同步辐射。我们报告了改进的电离能，并表征了单重态和三重态的离子基态和激发态。振动结构是根据计算的几何形状和振动频率进行模拟的，从而深入了解电离时的几何形状变化。