【摘要】 用密度泛函理论方法研究了过亚硝酸在水溶液中的异构化反应机理 .在B3LYP/6 3 1G(d)水平基础上用梯度解析技术全自由度优化了反应物、产物和反应途径中的中间产物及过渡态的几何构型 ,并通过振动频率分析加以确认 ,进行了内禀反应坐标 (IRC)计算 ,确定了该反应的可能通道 .结果表明 :该反应为多通道强放热反应 ,其中以羟基直接转移途经能垒最小 ,绝对反应速率常数值最大 ,因此 ,推测该通道为主要的反应通道更多还原

【Abstract】 The isomerization mechanism of peroxynitrous acid (ONOOH) in the aqueo us solution has been studied by using density function theory. The geometries of reactants, transition states, intermediates and products have been optimized by B3LYP/6-31G(d) basis set and verified by frequency analysis. The reaction path w ay was traced by Fukui’s theory of intrinsic reaction coordinate (IRC). The reac tion channels were verified. The study shows that the isomerization reaction is a multi-step and multi-channel complex one, and highly exothermic. Among them the channel (1) is a principal one. The activation energy is 129.9 kJ /mol. The absolute rate constant is 1.95×10 -10 s -1 .更多还原