CAJ | 학술논문

采用密度泛函UB3LYP／6—311＋G（2d）方法计算研究了Zn^＋离子与NO2的反应机理以及Zn^＋离子与CO、N2O的循环催化反应机理．全参数优化了反应势能面上各驻点的几何构型．用UB3LYP／6—311＋＋G（3df，3pd）方法对各驻点作了单点能量计算．计算结果表明：在Zn^＋与NO2的反应以及Zn^＋与CO、N2O的反应中，激发态的四重态Zn^＋（4s^13d^94p^1，^4F）的能量比二重态Zn^＋（4s^13d^10，^2S）的能量高1377．87kJ／mol，基态。Zn^＋离子与NO2的反应为一步反应，基态。Zn^＋离子与CO、N2O的反应为两步反应，且反应机理都为插入消去反应．
채용밀도범함UB3LYP／6—311＋G（2d）방법계산연구료Zn^＋리자여NO2적반응궤리이급Zn^＋리자여CO、N2O적순배최화반응궤리．전삼수우화료반응세능면상각주점적궤하구형．용UB3LYP／6—311＋＋G（3df，3pd）방법대각주점작료단점능량계산．계산결과표명：재Zn^＋여NO2적반응이급Zn^＋여CO、N2O적반응중，격발태적사중태Zn^＋（4s^13d^94p^1，^4F）적능량비이중태Zn^＋（4s^13d^10，^2S）적능량고1377．87kJ／mol，기태。Zn^＋리자여NO2적반응위일보반응，기태。Zn^＋리자여CO、N2O적반응위량보반응，차반응궤리도위삽입소거반응．
The reaction mechanism between Zn+ with CO, N20 and NO2 in ground state is studied using the density functional theory (DFT) at UB3LYP/6-311+G(2d) level. The geometries for reactants, the transition states and the products were completely optimized. All the transition states were verified. For each sta tionary point, single-point energy calculations were carried out by UB3LYP/6-311++G(3df, 3pd) method. The calculation results show that the energy of the quartet states Zn+ (4s^13d^94p^1 ,^4 F) is more 1 377.87 kJ/mol than the energy of double states Zn^+ (4s^13d^10 ,^2S), the reaction is a one step reaction NO2 with double states Zn^+ and the reaction is a two-step reaction CO and N2O with double states Zn+ , the reaction mechanism is an insertion elimination mechanism.