Threshold photoelectron spectroscopy of organosulfur radicals†

IF 2.9 3区化学 Q3 CHEMISTRY, PHYSICAL

Physical Chemistry Chemical Physics Pub Date : 2024-11-05 DOI:10.1039/D4CP03906H

Emil Karaev, Marius Gerlach, Dorothee Schaffner, Sarah E. Dutton, Maggie D. Phillips, Patrick Hemberger, AnGayle K. Vasiliou and Ingo Fischer

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Abstract

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.

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有机硫自由基的阈值光电子能谱学

我们报告了几种含硫反应中间体的振动分辨阈值光电子能谱。其中包括与大气化学和天体化学环境相关的有机硫自由基 CH2S、CH3S、CH2SH、CH3S2 和 S2H。由于反应活性高，这些自由基是通过热解 (CH3)2S2 在原位制备的。利用光电子-光电子重合装置（PEPICO）和瑞士光源的同步辐射，通过光电子质量选择阈值光电子能谱分析了有机硫的特征。我们报告了改进的电离能，并描述了离子基态和激发态（包括单重态和三重态）的特征。根据计算出的几何形状和振动频率模拟了振动结构，从而深入了解了电离时几何形状的变化。

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来源期刊

Physical Chemistry Chemical Physics 化学-物理：原子、分子和化学物理

CiteScore

5.50

自引率

9.10%

发文量

2675

审稿时长

2.0 months

期刊介绍： Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.