HCO+NO_2反应势能面的理论研究

Theoretical Studies on Reaction Potential Energy Surface of the Formyl Radical with Nitrogen Dioxide

在 B3 LYP/6-3 1 1 G( d,p)和 CCSD( T) /6-3 1 1 G( d,p)水平上给出了 HCO+NO2 反应详细的势能面信息 .计算结果表明 ,该反应采用两种无垒进攻方式 ,分别得到两种加合物 H( O) CNO2 和 H( O) CONO.找到7种能量低于反应物且合理的产物及相应的反应路径 .通过对热力学和动力学的分析 ,产物 HONO+CO( P2 ,P3 ) ,HNO+CO2 ( P1 )和 H+CO2 +NO( P6)的形成更为有利 .计算结果同实验相符 ,且有助于深入了解 HCO自由基的化学行为 .

The detail singlet potential energy surface of the HCONO 2 system is investigated at the B3LYP and CCSD(T)(single-point) levels with 6-311G(d,p) basis set to study the possible reaction mechanism of HCO with NO 2. From the reactant R(HCO+NO 2), two associated adducts HC(O)NO 2 and H(O)CONO can be formed barrierlessly. Possible energetically allowed reaction pathways leading to seven low-lying dissociation products. The formation of HONO+CO(P2,P3), HNO+CO 2(P1) and H+CO 2+NO(P6) are more favorable than other products on the consideration of kinetic and thermodynamic factors. The calculated results presented in this paper agree with the previous experiment investigations and may be helpful for understanding this chemical behavior of formyl radical.