Chemical Physics Letters ( IF 2.8 ) Pub Date : 2020-08-06 , DOI: 10.1016/j.cplett.2020.137846 S. Kuzhanthaivelan , B. Rajakumar
The reaction kinetics of dimethoxymethane (DMM) towards H atom abstraction by hydroperoxy and methyl peroxy radicals were investigated using the G4 composite method. All the studied reactions were found to be endothermic and non-spontaneous in nature. Canonical Variational Transition State Theory in combination with Small Curvature Tunneling corrections were adopted to calculate the rate coefficients in the temperature range of 400–1500 K. The Arrhenius expressions for the reaction of DMM with CH3OO and HO2 radicals were obtained as ktotal = 1.50 × 10−12 exp (−8159/T) and ktotal = 4.40 × 10−12 exp (−7251/T) cm3 molecule−1 s−1 respectively.
中文翻译:
二甲氧基甲烷与过氧自由基动力学的理论研究
使用G4复合方法研究了二甲氧基甲烷(DMM)通过氢过氧和甲基过氧自由基夺取H原子的反应动力学。发现所有研究的反应本质上都是吸热的和非自发的。采用典型变分过渡态理论结合小曲率隧穿校正来计算400–1500 K温度范围内的速率系数。获得了DMM与CH 3 OO和HO 2自由基反应的Arrhenius表达式,共计k = 1.50×10 -12 exp(−8159 / T),k total = 4.40×10 -12 exp(−7251 / T)cm 3分子-1s -1。