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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Thionyl Fluoride from Sulfur Hexafluoride Corona Discharge Decomposition: Gas-Phase Chemistry of [SOF_2]H~+ Ions
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Thionyl Fluoride from Sulfur Hexafluoride Corona Discharge Decomposition: Gas-Phase Chemistry of [SOF_2]H~+ Ions

机译：六氟化硫电晕放电分解中的亚硫酰氟：[SOF_2] H〜+离子的气相化学

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摘要

Thionyl fluoride (SOF_2) is one of the major sulfur hexafluoride (SF_6) decomposition products under electric discharges. The protonation of SOF_2 produced by corona discharge of SF_6/air mixtures has been studied by the joint application of mass-spectrometric and ab initio theoretical methods. The structurally diagnostic collisionally activated dissociation (CAD) and Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometric results point to the formation of a mixed population of [SOF_2]H~+ protomers, the HF-SOF~+ ion-molecule complex (II), which reacts with selected nucleophiles as SOF~+ donor, and the covalently bounded H-OSF_2~+ species (I), which behaves as a protonating agent. Computational results at the B3LYP and CCSD(T) levels of theory show that the stability of isomer I exceeds that of II by 7.6 and 5.4 kcal mol~(-1), respectively, whereas the energy barrier for their interconversion is computed to be as large as 45.2 kcal mol~(-1) at B3LYP level. The proton affinity of thionyl fluoride is estimated from FT-ICR "bracketing" experiments to be 157.7 ± 3 kcal mol~(-1), consistent with the value obtained from theoretical calculation at B3LYP and CCSD(T) levels of theory, 153.6 ± 3 and 155.5 ± 3 kcal mol~(-1), respectively.
机译：亚硫酰氟（SOF_2）是放电时主要的六氟化硫（SF_6）分解产物之一。通过质谱和从头算理论方法的联合应用，研究了SF_6 /空气混合物的电晕放电产生的SOF_2的质子化。结构诊断碰撞活化解离（CAD）和傅立叶变换离子回旋共振（FT-ICR）质谱结果表明，形成了[SOF_2] H〜+原型分子HF-SOF〜+离子分子复合物的混合群（II），其与选定的亲核试剂反应为SOF〜+供体，和共价键合的H-OSF_2〜+种类（I），其充当质子化剂。理论上的B3LYP和CCSD（T）水平的计算结果表明，异构体I的稳定性分别比II的稳定度高7.6和5.4 kcal mol〜（-1），而互变的能垒计算如下：在B3LYP水平下最大为45.2 kcal mol〜（-1）。亚硫酰氟的质子亲和力通过FT-ICR“包围”实验估计为157.7±3 kcal mol〜（-1），与B3LYP和CCSD（T）理论水平的理论计算值153.6±一致。分别为3和155.5±3 kcal mol〜（-1）。

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