亚硝酰氢与羟基自由基反应的密度泛函理论研究

用密度泛函理论研究了HNO OH反应机理。在(U)B3LYP/aug-cc-pVTZ水平上,优化了反应通道上各驻点(反应物、中间体、过渡态和产物)的几何构型,获得了零点能校正后的反应势能曲线。研究表明:根据进攻方式的不同,有3个反应通道,反应通道不同则产物不同。反应的主要产物是NO H_2O,次要产物是NH_2 O_2;主要产物和次要产物与反应物的总能量之差(经零点能校正后)分别为-133.42 kJ/mol和150.44 kJ/mol。生成主要产物时主要反应通道的活化能为102.11 kJ/mol。

A density functional theoretical study of the reaction of HNO with OH radical

Using the density functional theory(DFT),the reaction mechanism for the HNO OH reaction was studied.The geometries of stationary points(reactants,transition states,isomers and productions)were optimized at the(U)B3LYP/aug-cc-pVTZ level.The potential energy surfaces(PES)for the HNO OH reaction were obtained with the corrections of zero-point vibrational energies.The calculated results suggested that the attacking way of the OH radical to HNO have three pathways,NO H_2O is the main product by the analysis of the change of the HNO OH reaction energies and NH_2 O_2 is the secondary product.The relative energies of the main and secondary products with respect to that of the reactants are-133.42 kJ/mol and 150.44 kJ/mol,respectively.The activation barrier of the dominant reaction pathway was predicted to be 102.11 kJ/mol.