Thioformaldehyde S-Sulfide, Sulfur Analogue of the Criegee Intermediate: Structures, Energetics, and Rovibrational Analysis,The Journal of Physical Chemistry A

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Thioformaldehyde S-Sulfide, Sulfur Analogue of the Criegee Intermediate: Structures, Energetics, and Rovibrational Analysis
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2017-01-27 00:00:00 , DOI: 10.1021/acs.jpca.6b12473
Kevin V. Murphy ₁ , Whitney J. Morgan ₁ , Zhi Sun ₁ , Henry F. Schaefer ₁ , Jay Agarwal ₁

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The ephemeral Criegee intermediate, first postulated over 70 years ago, has only recently been isolated in the gas phase. The sulfur analogue of this canonical zwitterion, thioformaldehyde S-sulfide, has eluded similar analysis; however, argon matrix isolation has been achieved ( Angew. Chem., Int. Ed. 2001, 40, 393−396). Here thioformaldehyde S-sulfide and its valence isomer dithiirane are examined with high-level coupled-cluster methods, including the minimum-energy pathway for interconversion. Relative enthalpies calculated from extrapolated energies at the complete basis set limit of the full CCSDTQ method are reported. Isomerization from thioformaldehyde S-sulfide to the lower-lying dithiirane (−7.2 kcal mol^–1) is predicted to include a 27.0 kcal mol^–1 barrier. Harmonic and anharmonic vibrational frequencies are also predicted using second-order vibrational perturbation theory. These results should aid in future gas-phase identification.

中文翻译：

硫代甲醛S-硫化物，Criegee中间体的硫类似物：结构，能级和振动分析

短暂的Criegee中间体最早假定于70多年前，直到最近才在气相中被分离出来。这种标准的两性离子的硫类似物，硫代甲醛S-硫化物，尚无类似分析。然而，氩矩阵隔离已经实现（Angew化学杂志，中间体版 2001，40，393-396）。在这里，采用高级偶联簇方法（包括互变的最小能量途径）对硫代甲醛S-硫化物及其化合价异构体二硫杂环戊烷进行了研究。报告了在完全CCSDTQ方法的完整基准集极限下根据外推能量计算出的相对焓。硫代甲醛S的异构化硫化物到较低位置的二硫代ane烷（-7.2 kcal mol ^-1）预计将包含27.0 kcal mol ^-1的势垒。还使用二阶振动摄动理论来预测谐波和非谐振动频率。这些结果将有助于将来的气相鉴定。

更新日期：2017-01-27

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