基于同步辐射真空紫外光电离质谱和高精度理论计算的乙炔燃烧动力学研究

Acetylene is an important intermediate in the combustion of hydrocarbon fuels and one of the precursors of soot formation, which plays a key role in the formation mechanism of polycyclic aromatic hydrocarbons. Developing an accurate combustion kinetic model for acetylene can help developing the core mechanism of C0-C4 combustion and the formation mechanism of polycyclic aromatic hydrocarbons. However, the mechanism of acetylene combustion is not accurate enough, and the improvements on the rate constants of key reactions, and kinetic models are very demanding. By combining theory and experiment, in this project, we will study the detailed combustion dynamics of acetylene. Experimentally, the combustion products and intermediates will be detected using the SVUV-PIMS combined with molecule beam sampling technique to obtain information for the radicals and isomers existed in the laminar premixed flame which are very essential for combustion kinetic models. Theoretically, we will construct the global potential energy surfaces for the C2H2+H/OH/HO2 reactions using high-level ab initio method and permutation invariant polynomial neural network approach. The reaction dynamics will be investigated using quasi-classical trajectory or ring polymer molecular dynamic method to obtain accurate rate constants and quantum state resolved dynamic information and reveal the detailed microscopic mechanism of acetylene combustion. Besides, kinetic model for acetylene combustion which can be applied in wide operating conditions will be developed to provide guidance for further experimental and theoretical studies and help developing the kinetic model for real fuels.

乙炔是碳氢燃料燃烧过程中重要的中间体，是碳烟生成的前驱体之一，对多环芳烃的生成和生长起着关键作用。发展高精度乙炔燃烧动力学模型，可为C0-C4核心机理和多环芳烃生长机理的构建和发展提供支持。目前乙炔燃烧机理中关键反应的速率常数仍不够精确，动力学模型有待进一步完善。本项目拟通过理论与实验的紧密结合，深入研究乙炔的燃烧动力学机制。利用同步辐射真空紫外光电离质谱结合超声分子束取样技术研究乙炔层流预混火焰，对燃烧产物和中间体进行在线检测，获取自由基等不稳定中间体和同分异构体信息，为动力学模型发展提供丰富的实验数据。构建C2H2+H/OH/HO2等反应的高精度势能面，采用准经典轨迹和环聚合物分子动力学方法获得高精度的速率常数和产物量子态分布等性质，揭示乙炔燃烧过程中细致的微观动力学机制。发展适用于宽工况的高精度乙炔燃烧动力学模型，为进一步实验和理论研究提供指导，为实际燃料燃烧动力学模型的发展提供帮助

乙炔是碳氢燃料燃烧过程中重要的中间体，是碳烟生成的前驱体之一，对多环芳烃的生成和生长起着关键作用。发展高精度乙炔燃烧动力学模型，可为C0-C4核心机理和多环芳烃生长机理的构建和发展提供支持。然而，乙炔燃烧机理中关键反应的速率常数目前仍不够精确，动力学模型有待进一步完善。本项目开展了与乙炔燃烧密切相关的关键化学反应的动力学性质的实验和理论研究，深入研究了乙炔的燃烧动力学机制。实验上，获得了不同当量比条件下的乙炔层流预混火焰中产物和中间体分布的摩尔分数，获得大量燃烧产物与中间体在火焰中的空间分布情况。理论上，构建了C2H2+O/OH/HO2以及HO2+O等反应体系的高精度全维势能面，采用环聚合物分子动力学或准经典轨迹方法获得了高精度的速率常数和产物量子态分布等性质，对反应机理以及微观动力学机制进行了详细的探讨，并揭示了其在乙炔燃烧过程中的重要作用。上述工作有助于进一步构建和发展适用于宽工况的高精度乙炔燃烧动力学模型，为C0-C4核心机理的发展提供支持，进而为实际燃料燃烧动力学模型的发展提供帮助。相关工作在国际重要学术期刊发表研究论文12篇，包括Nat. Commun. 1 篇 J. Phys. Chem. Lett. 3篇，Combust. Flame 1篇，J. Phys. Chem. A/C 2篇, Phys. Chem. Chem. Phys. 1篇，J. Chem. Phys. 1篇等。此外，本人曾3次受邀在国内学术会议上做报告，并合作培养了2名博士研究生。