论文部分内容阅读
应用密度泛函理论研究了反应通道(a)C2H3+NO→CH3+NCO和(b)C2H3+NO→OH+C2H2N的反应机理.在B3LYP/6-31G(d)水平上优化了反应物、中间体、过滤态、产物的几何构型,通过频率分析确定了11个中间体和10个过渡态.所有的反应物、中间体、过渡态、产物都在CCSD/6-311++G(d,p)水平上进行了单点能较正.并讨论了反应的异构化过程.计算结果表明10是能量最低的中间体,比反应物的能量低308 479kJ/mol;过渡态1/3,2/5,3/4,4/8比反应物的能量高,其中3/4是能量最高的过渡态,比反应物的能量高91 894kJ/mol.通道(a)和(b)的理论放热值分别为111 059和96 619kJ/mol.
The reaction mechanism of C2H3 + NO → CH3 + NCO and (b) C2H3 + NO → OH + C2H2N was studied by using density functional theory. The reactants were optimized at B3LYP / 6-31G (d) Intermediates, filtered states and product geometries, 11 intermediates and 10 transition states were determined by frequency analysis.All reactants, intermediates, transition states and products were determined by CCSD / 6-311 ++ G ( d, p), and the isomerization process of the reaction was discussed.The calculated results show that 10 is the lowest energy intermediate, which is 308 479 kJ / mol lower than that of the reactants, and the transition state 1 / 3, 2/5, 3/4, and 4/8 are energetically higher than the reactants, of which 3/4 are the most energetic transition states, 91 894 kJ / mol higher than the reactants. Channels (a) and (b) The theoretical exothermic values were 111 059 and 96 619 kJ / mol, respectively.