HClO的结构及其异构化反应机理的理论研究

A Theoretical Study of the Structural and Isomerization Reaction of HClO

用MP2方法和密度泛函方法研究了HOCl与HClO间的异构化反应机理,找到了反应的过渡态,用MP2方法和几种密度泛函方法计算得到的结果,以及在密度泛函方法中用不同的基组计算所得的结果与实验值进行比较,研究发现MP2方法计算的结果优于密度泛函方法计算的结果,而用密度泛函方法计算的结果中基组越大其计算结果与实验值符合得越好。同时发现HOCl及其异构体HClO都具有Cs对称性,HOCl异构化为HClO的反应活化能较大(320.0kJ/mol),说明HOCl异构体较稳定。

The isomerization reactant mechanism of HOCl→HClO has been studied by means of MP2 and density functional theory(DFT), and the transition state of this reaction has been found. It is found out that the outcome of the calculation with MP2 is superior to that with density function theory methods and that the larger the base cluster is, the more the calculated outcome fits its experimental value. It has been found out, too, that HOCl and its isomerization HClO both are characteristic of asymmetry. HOCl is made isomeric as HClO, whose reactant activation energy is strong (320.0 kJ/mol), showing that the isomerization HOCl is steady.