The microcosmic reaction mechanism of the thermal decomposition of potassium nitroformate（KNF） has been investigated by density functional theory within the generalized gradient approximation. The geometric structur...The microcosmic reaction mechanism of the thermal decomposition of potassium nitroformate（KNF） has been investigated by density functional theory within the generalized gradient approximation. The geometric structures of reactants, intermediates, transition states, and products are fully optimized. The frequency analysis approves the authenticity of intermediates and transition states. Our results show that there are four feasible reaction pathways. The main pathway of the reaction is KNF → B1 → TSB1 → B2 → TSB2 → B3 → TSB3 → B4 → KNO2 ＋ NO2 ＋ NO ＋ CO, and the energy barrier of the rate-limiting step is 216.30 k J·mol^-1. The dominant products predicted theoretically are KNO2, NO2, NO, and CO, which is in agreement with the experiment.展开更多
基金supported by the Scientific and Technological Research Program of Chongqing Municipal Education Commission(KJ131318,KJ1401227,KJ15012002)the Fuling Science and Technology Commission(FLKJ2015ABA1042)the Project of Chongqing Key Laboratory of Inorganic Special Functional Materials(KFKT201506)
文摘The microcosmic reaction mechanism of the thermal decomposition of potassium nitroformate（KNF） has been investigated by density functional theory within the generalized gradient approximation. The geometric structures of reactants, intermediates, transition states, and products are fully optimized. The frequency analysis approves the authenticity of intermediates and transition states. Our results show that there are four feasible reaction pathways. The main pathway of the reaction is KNF → B1 → TSB1 → B2 → TSB2 → B3 → TSB3 → B4 → KNO2 ＋ NO2 ＋ NO ＋ CO, and the energy barrier of the rate-limiting step is 216.30 k J·mol^-1. The dominant products predicted theoretically are KNO2, NO2, NO, and CO, which is in agreement with the experiment.
