A Data-Inspired and Physics-Driven Model Reduction for Dissociation: Application to O2+O System.
A Data-Inspired and Physics-Driven Model Reduction for Dissociation: Application to O2+O System.
复制标题
数据启发和物理驱动的解离模型还原：在 O2 O 系统中的应用。
DOI：
10.1021/acs.jpca.0c04516
复制
发表时间：
2020
期刊：
影响因子：
--
通讯作者：
M. Panesi
中科院分区：
文献类型：
--
作者：
Simone Venturi;Maitreyee P Sharma;B. Lopez;M. Panesi
结合准经典轨道计算、主方程和降维方法，对O2分子与O原子碰撞的非平衡解离过程进行了深入的讨论.通过在QCT计算中包括O3的所有九个绝热电子态，构建了所有基本碰撞过程的振转分辨数据库。从头算数据集的详细分析表明，对于振转能级，解离的概率主要取决于其内部能量的赤字相比，离心屏障。由于转动平衡的假设，传统的振动特定的计算无法表征这种依赖性。基于这一观察，提出了一种新的基于物理的分组策略应用于粗粒度模型。通过依赖于一种混合技术的振转分辨激发耦合到粗粒解离，新的方法相比，振动特定的模型和直接解决方案的振转状态到状态的主方程。模拟是在一个零维等温和等容化学反应器中进行的，温度范围很宽（1,500 - 20,000 K）。研究表明，振动特定的方法的模型不足的主要贡献源于无法表征解离，而不是能量转移。即使构建只有20组，新的降阶模型优于振动特定的一个在预测所有的相关的解离动力学的生活质量。在最高温度下，摩尔分数的精度提高了2000%。
This work presents an in-depth discussion on the non-equilibrium dissociation of O2 molecules colliding with O atoms, combining quasi-classical trajectory calculations, master equation, and dimensionality reduction. A rovibrationally-resolved database for all of the elementary collisional processes is constructed by including all nine adiabatic electronic states of O3 in the QCT calculations. A detailed analysis of the ab initio data set reveals that, for a rovibrational level, the probability of dissociating is mostly dictated by its deficit in internal energy compared to the centrifugal barrier. Due to the assumption of rotational equilibrium, the conventional vibrational-specific calculations fail to characterize such a dependence. Based on this observation, a new physics-based grouping strategy for application to coarse-grained models is proposed. By relying on a hybrid technique made of rovibrationally-resolved excitation coupled to coarse-grained dissociation, the new approach is compared to the vibrational-specific model and the direct solution of the rovibrational state-to-state master equation. Simulations are performed in a zero-dimensional isothermal and isochoric chemical reactor for a wide range of temperatures (1,500 - 20,000 K). The study shows that the main contribution to the model inadequacy of vibrational-specific approaches originates from the incapability of characterizing dissociation, rather than the energy transfers. Even when constructed with only twenty groups, the new reduced-order model outperforms the vibrational-specific one in predicting all of the QoIs related to dissociation kinetics. At the highest temperature, the accuracy in the mole fraction is improved by 2000%.