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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Facile Formation of Acetic Sulfuric Anhydride: Microwave Spectrum, Internal Rotation, and Theoretical Calculations
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Facile Formation of Acetic Sulfuric Anhydride: Microwave Spectrum, Internal Rotation, and Theoretical Calculations

机译：醋酸乙酸酐的容易形成：微波谱，内部旋转和理论计算

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Acetic sulfuric anhydride, CH3COOSO2OH, was produced by the reaction of SO3 and CH3COOH in a supersonic jet. Four isotopologues were observed by microwave spectroscopy. Spectra of both A and E internal rotor states were observed and analyzed, yielding a value of 241.093(3Q) cm(-1) for the methyl group internal rotation barrier of the parent species. Similar values were obtained for the other isotopologues studied. M06-2X/6-311+ +G(3df,3pd) calculations indicate that the formation of the anhydride proceeds via a pi(2) +pi(2) + sigma(2) cycloaddition reaction within the CH3COOH-SO3 complex. The equilibrium orientation of the methyl group relative to the O=C-C plane is different in the anhydride and in the CH3COOH-SO3 complex, indicating that the -CH3 internal rotation accompanies the cycloaddition reaction. The energies of key points on the potential energy surface were calculated using CCSD(T)/complete basis set with double and triple extrapolation [CBS/(D-T)], and the transformation from the CH3COOH-SO3 complex to CH3COOSO2OH is shown to be nearly barrierless regardless of the orientation of the methyl group. This study provides the second experimental observation of the reaction between a carboxylic acid and SO3 to form a carboxylic sulfuric anhydride in the gas phase. Possible connections to atmospheric aerosol formation are discussed.
机译：通过在超声射流中的SO 3和CH 3 COOH的反应产生乙酸硫酸酐CH3COOSO 2 OH。通过微波光谱观察到四同位素。观察和分析A和E内转子状态的光谱，得到母体物种的甲基内旋转屏障的241.093（3Q）cm（-1）的值。为所研究的其他同位素获得类似的值。 M06-2X / 6-311 + G（3DF，3PD）计算表明，酸酐的形成通过CH 3 COOH-SO3复合物内的PI（2）+ Pi（2）+σ（2）环加成反应进行。甲基相对于O = C-C平面的平衡取向在酸酐和CH 3 COOH-SO3复合物中不同，表明-CH3内旋转伴随着环加成反应。潜在能量表面上的关键点的能量/三重外推的CCSD /完全基础（CBS /（DT）]计算，并且从CH3COOH-SO3复合物到CH3COOSO 2OH的转化近无论甲基的取向如何，障碍无论。该研究提供了羧酸和SO 3之间反应的第二实验观察，以在气相中形成羧酸硫酸酐。讨论了与大气气溶胶形成的可能连接。

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