Chen N L, Gans B, Boyé-Péronne S, Hartweg S, Garcia G A, Loison J-C
Université Paris-Saclay, CNRS, Institut des Sciences Moléculaires d'Orsay, F-91405 Orsay, France.
Synchrotron SOLEIL, L'Orme des Merisiers, St. Aubin, F-91192 Gif sur Yvette, France.
J Chem Phys. 2024 Mar 21;160(11). doi: 10.1063/5.0198424.
SiCH and its cation have consistently emerged as predicted species in models of silicon chemistry within the interstellar medium, although they remain unobserved in space. Hindered by their intrinsic instability, no spectroscopic insights have been gleaned concerning the SiCH+ cation. In this study, we present experimental measurements on the SiCH+ cation through single-photon ionization spectroscopy of the SiCH radical within the 8.0-11.0 eV range. Gas-phase SiCH radicals were generated through chemical reactions involving CHx (x = 0-3) and SiHy (y = 0-3) within a microwave discharge flow-tube reactor. Employing a double imaging photoelectron/photoion coincidence spectrometer on the DESIRS beamline at the SOLEIL synchrotron, we recorded mass-selected ion yield and photoelectron spectra. From the analysis of the photoelectron spectrum supported by ab initio calculations and Franck-Condon simulations, the adiabatic ionization energies for the transitions from the X2Π ground electronic state of SiCH toward the X+3Σ- and A+3Π electronic states of SiCH+ have been derived [8.935(6) and 10.664(6) eV, respectively, without spin-orbit correction]. The contribution from the less stable isomer HSiC has been explored in our analysis and ruled out in our experiments.
硅碳氢(SiCH)及其阳离子一直以来都是星际介质中硅化学模型预测出的物种,尽管它们在太空中仍未被观测到。由于其内在的不稳定性,尚未获得关于SiCH⁺阳离子的光谱学见解。在本研究中,我们通过对8.0 - 11.0电子伏特范围内的SiCH自由基进行单光子电离光谱,给出了关于SiCH⁺阳离子的实验测量结果。气相SiCH自由基是在微波放电流动管反应器中通过涉及CHₓ(x = 0 - 3)和SiHy(y = 0 - 3)的化学反应产生的。利用SOLEIL同步加速器DESIRS光束线上的双成像光电子/光离子符合光谱仪,我们记录了质量选择离子产率和光电子能谱。通过从头算计算和弗兰克 - 康登模拟支持的光电子能谱分析,得出了SiCH从X²Π基电子态跃迁到SiCH⁺的X⁺³Σ⁻和A⁺³Π电子态的绝热电离能[分别为8.935(6)和10.664(6)电子伏特,无自旋 - 轨道校正]。在我们的分析中探讨了较不稳定异构体HSiC的贡献,并在实验中排除了其影响。