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采用密度泛函UB3LYP方法和Stuttgart赝势基组,计算研究了气相中循环催化N2O(X1∑)++CO(1∑)+→N2(X1∑g)++CO2(1∑g)+反应的微观机理.通过对相关物种亲氧性的计算,证明了Ir+循环催化作用在热力学上是可行的.不同自旋态反应势能面的计算结果表明,循环催化的两步反应均为自旋禁阻反应,各存在不同自旋态势能面的交叉,并运用Yoshizawa的内禀坐标单点垂直激发计算的方法找出了势能面交叉点;两步反应均为放热反应,总放热量为358.9kJ·mol-1.
The cyclic catalytic N2O (X1Σ) ++ CO (1Σ) + → N2 (X1Σg) ++ CO2 (1Σg) + reaction in the gas phase was investigated by using the density functional UB3LYP method and the Stuttgart pseudopotential base. The results show that the Ir + cycle catalysis is thermodynamically feasible.According to the calculated results of the potential energy surfaces of different spin states, the two-step reactions of the cyclic catalysis are both spin-forbidden Resistance reaction, the existence of different spin state potential energy surface cross, and the use of Yoshizawa’s intrinsic coordinate single-point vertical excitation calculation method to find the intersection of potential energy surface; both reactions are exothermic reaction, the total heat release is 358.9kJ · Mol-1.