苯甲醛脱氢反应从头算及速率系数不确定度分析  

Ab-initio Calculation of H-Atom Abstractions of Benzaldehyde and Uncertainty Analysis of Rate Coefficient

作　　者：赵浩 张英佳[1] 黄佐华[1] Zhao Hao;Zhang Yingjia;Huang Zuohua(State Key Laboratory of Multiphase Flow in Power Engineering,Xi’an Jiaotong University,Xi’an 710049,China)

机构地区：[1]西安交通大学动力工程多相流国家重点实验室,西安710049

出　　处：《燃烧科学与技术》2022年第1期78-84,共7页Journal of Combustion Science and Technology

基　　金：国家自然科学基金资助项目(91741115).

摘　　要：在计算水平下(CCSD(T)/cc-pVTZ/M06-2X/6-311+g(d,p)),采用RRKM/ME方法,考虑了范德瓦尔斯势阱反应通道,开展了苯甲醛与H/Ö/OH/CH_(3)/HO_(2)/O_(2)自由基的脱氢反应速率系数理论计算,计算获得的苯甲醛+OH脱氢反应总速率与Stanford实验测量结果吻合较好;并通过随机取样法评估了计算速率系数不确定度.对比乙醛同类型反应,H原子和HO_(2)自由基脱氢反应速率系数在误差范围内保持一致,但OH自由基脱氢规律完全相反,理论上证实了过去类比乙醛描述苯甲醛+OH脱氢反应速率系数的不合理性.The H-atom abstractions of benzaldehyde by H/Ö/OH/CH_(3)/HO_(2)/O_(2) are calculated by the RRKM-Master Equation at CCSD(T)/cc-pVTZ//M06-2X/6-311+g(d,p)level to predict reaction rate coefficients.The calculated rate coefficients of benzaldehyde+OHare generally in good agreement with literature measurements.A random sampling method is used to estimate the global uncertainty.A comparison between benzaldehyde and acetaldehyde reveals that their rate coefficients are consistent only in H-abstractions by H and HO_(2),but con-flictive in other reactions,especially in the case of OHattacking.This study theoretically proves the unreason-ableness of direct analogy of H-atom abstraction reactions of benzaldehyde from acetaldehyde.

关 键 词：苯甲醛 脱氢反应速率 量子化学从头算 RRKM主方程 不确定度分析 

分 类 号：TK16[动力工程及工程热物理—热能工程]