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本文采用密度泛函理论DFT-UB3LYP方法,在6-311+G(2d)和6-311+G(2d,p)的基组下,计算研究了气相中Ca~+离子介入N_2O(~1∑~+)和CO(~1∑~+)与N_2O(~1∑~+)和H_2(~1∑_g~+)反应的微观机理.报道了二重态势能面上各反应物、中间体和过渡态的构型特征及能量,并用频率分析和内禀反应坐标(IRC)方法对过渡态进行了验证.计算结果表明,金属离子参与N_2O和CO与N_2O和H_2的反应都分两步进行,其中Ca~+离子对反应N_2O(X~1∑~+)+CO(~1∑~+)生成N_2(X~1∑_g~+)+CO_2(~1∑_g~+)比较Fe~+,Ir~+,Pt~+等的金属离子有良好的催化作用,而对反应N_2O(X~1∑~+)}H_2(~1∑_g~+)→N_2(~1∑_g~+)+H_2O(~1A_1)催化作用不是很好,N_2、CaOH~+和H是该反应的主要产物,与实验观测结果相符,并通过对金属离子亲氧性(OA)的计算,从热力学方面进一步说明主题反应的可行性.
In this paper, the density functional theory (DFT-UB3LYP) method was used to study the effect of Ca ~ (+) ion on the concentration of N_2O in the gas phase under the groups of 6-311 + G (2d) and 6-311 + G The micro-mechanism of the reaction between CO ~ (1Σ ~ +) and N_2O (~ 1Σ ~ +) and H_2 (~ 1Σ_g ~ +) And transition states, and the transition state was verified by the frequency analysis and the intrinsic reaction coordinate (IRC) method.The calculated results show that the metal ions involved in the reaction of N 2 O and CO with N 2 O and H 2 are in two steps , In which Ca ~ + ion generated N_2 (~ 1Σ_g ~ +) + CO_2 (~ 1Σ_g ~ +) for the reaction of N_2O (X ~ 1Σ ~ +) +, Ir ~ +, Pt ~ + and other metal ions have a good catalytic effect on the reaction of N_2O (~ 1Σ ~ +)} H_2 (~ 1Σ_g ~ +) → N_2 (~ 1Σ_g ~ ) + H_2O (~ 1A_1) is not very good. N_2, CaOH ~ + and H are the main products of the reaction. The results are in good agreement with the experimental results. From the thermodynamic Further illustrate the feasibility of the subject response.