Different Catalytic Effects of a Single Water Molecule: The Gas-Phase Reaction of Formic Acid with Hydroxyl Radical in Water Vapor
Different Catalytic Effects of a Single Water Molecule: The Gas-Phase Reaction of Formic Acid with Hydroxyl Radical in Water Vapor
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DOI：
10.1002/cphc.200900387
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发表时间：
2009-12-07
期刊：
影响因子：
2.9
通讯作者：
Gonzalez, Javier
中科院分区：
文献类型：
--
作者：
Anglada, Josep M.;Gonzalez, Javier
采用DFT-B3 LYP、MP2和CCSD（T）理论方法，在6-311 +G（2df，2 p）和aug-cc-pVTZ基组下，研究了单个水分子对甲酸与羟基自由基气相反应机理的影响. HCOOH与HO之间的反应具有非常复杂的机理，涉及质子耦合电子转移过程（pcet）、两个氢原子转移反应（hat）和双质子转移过程（dpt）。羟基自由基主要通过pcet机制夺取甲酸的酸性氢。单个水分子以不同的方式影响这些反应机制中的每一个，这取决于水相互作用的方式。非常有趣的事实是，我们的计算预测，一个单一的水分子的参与导致在通过氢原子转移过程（帽子）的甲酸的甲酰基氢的抽象。
The effect of a single water molecule on the reaction mechanism of the gas-phase reaction between formic acid and the hydroxyl radical was investigated with high-level quantum mechanical calculations using DFT-B3LYP, MP2 and CCSD(T) theoretical approaches in concert with the 6-311 +G(2df,2p) and aug-cc-pVTZ basis sets. The reaction between HCOOH and HO has a very complex mechanism involving a proton-coupled electron transfer process (pcet), two hydrogen-atom transfer reactions (hat) and a double proton transfer process (dpt). The hydroxyl radical predominantly abstracts the acidic hydrogen of formic acid through a pcet mechanism. A single water molecule affects each one of these reaction mechanisms in different ways, depending on the way the water interacts. Very interesting is also the fact that our calculations predict that the participation of a single water molecule results in the abstraction of the formyl hydrogen of formic acid through a hydrogen atom transfer process (hat).