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首页> 外文期刊>RSC Advances >Water-catalysis in the gas phase reaction of dithioformic acid with hydroxyl radical: global reaction route mapping of oxidative pathways for hydrogen abstraction
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Water-catalysis in the gas phase reaction of dithioformic acid with hydroxyl radical: global reaction route mapping of oxidative pathways for hydrogen abstraction

机译：用羟基自由基二甲酸气相反应的水催化：氢气抽取氧化途径的全局反应路径映射

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摘要

The catalytic-role of water in the gas phase oxidation reaction of hydroxyl radical with dithioformic acid (DTFA) has been investigated through quantum mechanical computations performed using MP2, CCSD(T) and DFT methods. The pre-reaction complexes, which can considerably influence the thermodynamics and kinetics, are systematically explored through a global reaction route mapping (GRRM) method. The computations successfully revealed a positive catalytic role of water which is observed to stabilize the pre-reaction complexes as well as respective transition states, resulting in a significant lowering of the potential energy surface. The standard Gibbs free energy change for the explored pathways was also analyzed. The abstraction of acidic-hydrogen in DTFA was found to be both thermodynamically and kinetically more feasible than the formyl-hydrogen abstraction both in the presence and absence of water. Notably, a few of the pathways are observed to proceed through a proton-coupled electron-transfer mechanism. However, only formyl-hydrogen abstraction in the presence of water could be traced by all the different theoretical methods employed in this work.
机译：通过使用MP2，CCSD（T）和DFT方法进行的量子机械计算，研究了用二甲酸（DTFA）的羟基气相氧化反应的催化作用。通过全局反应路径映射（GRRM）方法，系统地探索能够大大影响热力学和动力学的预反应复合物。计算成功地显示出阳性催化作用，其观察到稳定预反应复合物以及各个过渡状态，导致潜在能量表面的显着降低。还分析了探索途径的标准GIBBS自由能量变化。发现DTFA中酸性氢的抽象在热力学上和动力学上比在存在和不存在水中的甲醛 - 氢气抽象中更加可行。值得注意的是，观察到少数途径以通过质子耦合的电子传递机构进行。然而，只有在水的情况下只有在水的情况下只能通过这项工作所采用的所有不同理论方法来追踪。

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  • 来源
    《RSC Advances》 |2015年第63期|共10页
  • 作者

    Kaur Gurpreet; Vikas;

  • 作者单位

    Panjab Univ Dept Chem Quantum Chem Grp Chandigarh 160014 India;

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  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类 化学;
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