气相中H_2O_2与N_2O反应机理的探讨

Theoretical Study on the Reaction Mechanism of H_2O_2 with N_2O

采用 RHF/AM1方法研究了 H_2O_2与 N_2O的反应机理 .计算结果表明 ,该反应是多步反应 ,先后通过 2个过渡态（ TS1,TS3） ,1个内旋转位垒（ TS2） ,2个中间体（ IM1,IM2） .其中从反应物 Re到 TS1为整个反应的决速步骤 ,速控步骤的活化能为 323.04 kJ· mol－ 1.整个反应为一放热反应 ,放出的热量为 147.67kJ· mol－ 1.

Greenhouse effect has been received more and more attention in the field of environment protection recently. N2O is an important geenhouse effect gas, whose effect is 206 times stronger than that of CO2. Some researches show that beacuse of coupling relationship and competition effect between different trace gases, other trace gases can affect N2O's life and ozone's depletion speed in the atmosphere. In order to give an instructive theoretical reference to experimental researchers, AM1 molecular orbital methods using the restricted Hartree-Fock (RHF) calculation have been applied to investigate the mechanism of the reaction of H2O2 with N2O. The results show that this is a multi-step reaction. Along the reaction path there are two transition states, one internal rotational barrier and two intermediates. The step from Re to IM1 is the rate-controlling step, whose activation energy is 323.04 kJ . mol(-1). The whole reaction is exothermic, with the heat of formation equals to - 147.67 kJ . mol(-1).