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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Dissociative photoionization of sulfur chlorides and oxochlorides: Thermochemistry and bond energies based on accurate appearance energies
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Dissociative photoionization of sulfur chlorides and oxochlorides: Thermochemistry and bond energies based on accurate appearance energies

机译：氯化硫和氯氧化物的解离光电离：基于精确外观能的热化学和键能

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The dissociative photoionization of four compounds, SCl_2, S _2Cl_2, SOCl_2, and SO_2Cl_2, were measured with threshold and imaging photoelectron photoion coincidence spectrometry (TPEPICO and iPEPICO). In all systems, the molecular ion loses a chlorine atom in a fast dissociation. The 0 K appearance energies of the first chlorine-loss fragment ions were determined to be 12.252 ± 0.012 eV, 11.205 ± 0.003 eV, 11.709 ± 0.003 eV, and 12.505 ± 0.003 eV, respectively. SCl_2 was measured on the laboratory-based TPEPICO instrument, in which the second Cl-loss dissociation could not be observed within the available photon energy. For S_2Cl_2~+ and SOCl_2~+, the appearance energy of the fragment ion after two chlorine-loss dissociations were determined to be 13.32 ± 0.02 eV and 14.88 ± 0.02 eV, respectively. On the basis of the analysis of the breakdown curves, it was concluded that assuming three-dimensional translational degrees of freedom yields a more reliable statistical model of the product energy distributions. The literature heat of formation of the neutral precursor molecule thionyl chloride, SOCl_2 does not agree with our results based on the SO~+ cation and is revised by more than 10 kJ mol~1 to 198.2 ± 2.4 kJ mol~1. A particularly broad FranckCondon gap with vanishingly small threshold electron signal in the photon energy range for the second Cl-loss reaction in SO_2Cl _2~+ is discussed with regard to the mechanism of threshold ionization.
机译：用阈值和成像光电子光合符合光谱法（TPEPICO和iPEPICO）测量了SCl_2，S_2Cl_2，SOCl_2和SO_2Cl_2这四种化合物的解离光电离。在所有系统中，分子离子都会以快速解离的方式失去氯原子。测定第一氯损失碎片离子的0 K出现能分别为12.252±0.012 eV，11.205±0.003 eV，11.709±0.003 eV和12.505±0.003 eV。 SCl_2是在基于实验室的TPEPICO仪器上测量的，其中在可用光子能量范围内未观察到第二次Cl损失解离。对于S_2Cl_2〜+和SOCl_2〜+，两次氯损失解离后碎片离子的出现能分别确定为13.32±0.02 eV和14.88±0.02 eV。在对击穿曲线的分析的基础上，得出的结论是，假设三维平移自由度会产生更可靠的产品能量分布统计模型。文献中关于中性前体分子亚硫酰氯SOCl_2的形成热与我们基于SO〜+阳离子的结果不一致，并且被修改了10 kJ mol〜1以上至198.2±2.4 kJ mol〜1。针对阈值电离的机理，讨论了一个特别宽泛的FranckCondon间隙，该阈值在光子能量范围内的阈值电子信号几乎消失，从而使SO_2Cl _2〜+中的第二次Cl损失反应。

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