Modeling third-body effects in the thermal decomposition of H2O2
Modeling third-body effects in the thermal decomposition of H2O2
复制标题
模拟 H2O2 热分解中的第三体效应
DOI：
10.1016/j.combustflame.2020.11.019
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发表时间：
2021
影响因子：
4.4
通讯作者：
Akira Matsugi
中科院分区：
文献类型：
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作者：
Kazuki Morita;Yuta Kizaki;Nobutsuna Endo;Norihiro Kamamichi;森田和希，遠藤信綱，釜道紀浩;木﨑裕太，遠藤信綱，釜道紀浩;木﨑裕太，遠藤信綱，釜道紀浩;森田和希，遠藤信綱，釜道紀浩;遠藤信綱;Akira Matsugi
用经典轨道法计算了H_2O_2在7种浴气（M = He，Ar，H_2，N_2，CO，CH_4，H_2O）中的碰撞能量传递过程，并对反应速率常数进行了主方程分析.能量传递过程采用指数下降模型的范围参数和能量传递的碰撞频率来模拟。这两个量的计算从碰撞轨迹上传播的势能面直接评估的优化自旋分量缩放MP2方法。主方程计算使用这些参数被发现在低压下的速率常数给出合理的描述。计算出的相对第三体效率与实验数据吻合良好的M = He，Ar，和N2，但计算的效率M = H2O似乎是高估在低温下。计算的速率常数用极限高压速率常数k ∞= 6.7 × 10 ~（14）exp表示（−24800 K/T）s−1，M = Ar和N2的极限低压速率常数k 0（Ar）= 3.65 × 108（T/K）−4.691exp（−26470 K/T）cm 3 molecule − 1 s − 1和k 0（N2）= 8.21 × 109（T/K）−5.034exp（−26600 K/T）cm 3 molecule − 1 s −1，Fcent的中心展宽因子= 0.7 exp（−T/3400 K），以及列表中的相对第三体效率。传统的线性混合规则合理地再现了多组分浴气体的压力依赖性速率常数计算，而混合规则的基础上减少的压力被发现提供了一个更精确的描述。
The thermal decomposition of hydrogen peroxide (H2O2) in seven bath gases (M = He, Ar, H2, N2, CO, CH4, and H2O) has been studied by classical trajectory calculations of the collisional energy transfer processes and master equation analyses of the pressure-dependent rate constants. The energy transfer processes are modeled with the range parameter of the exponential down model and collision frequency for energy transfer. Both of the two quantities are calculated from the collisional trajectories propagated on the potential energy surfaces directly evaluated by the optimized spin-component-scaled MP2 method. The master equation calculations using these parameters were found to give reasonable descriptions of the rate constants at low pressures. The calculated relative third-body efficiencies agree well with the available experimental data for M = He, Ar, and N2but the efficiency calculated for M = H2O appears to be overestimated at low temperature. The calculated rate constants are represented by the limiting high-pressure rate constant ofk∞= 6.7 × 1014exp(−24800 K/T) s−1, limiting low-pressure rate constants for M = Ar and N2ofk0(Ar) = 3.65 × 108(T/K)−4.691exp(−26470 K/T) cm3molecule−1s−1andk0(N2) = 8.21 × 109(T/K)−5.034exp(−26600 K/T) cm3molecule−1s−1, the center broadening factor ofFcent= 0.7 exp(−T/3400 K), and the tabulated relative third-body efficiencies. The pressure-dependent rate constants calculated for multicomponent bath gases are reasonably reproduced by the traditional linear mixture rule, whereas the mixture rule based on the reduced pressure is found to provide a more precise description.