当前位置:
X-MOL 学术
›
J. Phys. Chem. A
›
论文详情
Our official English website, www.x-mol.net, welcomes your
feedback! (Note: you will need to create a separate account there.)
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
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
Affiliation
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
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。