气体大分子燃料高精度理论热化学研究综述  

High-Level Theoretical Thermochemistry Study Review on Large Gaseous Fuel Molecules

作　　者：池奕承 张鹏[1] CHI Yi-cheng;ZHANG Peng(Deaprtment of Mechanical Engineering,The Hong Kong Polytechnic University,Hong Kong 999077,China)

机构地区：[1]香港理工大学机械工程学系

出　　处：《气体物理》2019年第5期32-42,共11页Physics of Gases

基　　金：国家自然科学基金“面向发动机的湍流燃烧基础研究”重大研究计划(91641105);香港理工大学研究基金(4-BCE8,G-YBXN)

摘　　要：由于日益严重的能源和环境问题,越来越多的研究者开始致力于提高发动机燃烧性能的研究.研究燃烧化学反应机理的目的是为了精确地预测和控制燃烧过程,从而提高燃烧效率,控制火焰稳定性以及优化排放.对于大分子燃料,通常采用类比的方法来估测其反应速率常数以构建其燃烧反应模型,但是这将会为模型带来较大的计算误差.为了更好地将大分子燃料应用在发动机中,对其进行高精度化学反应动力学研究是十分必要的.但是,由于目前广泛使用的高精度电子结构理论计算方法(如CCSD(T)/CBS和QCISD(T)/CBS)在处理这些大分子燃料上存在着巨大的困难,因此文章关注了目前可适用于大分子体系的高精度量化计算方法,并详细地介绍了其中一种适用于大分子体系的高精度量化计算方法ONIOM[QCISD(T)/CBS:DFT].该方法的提出不仅为研究大分子燃料体系的能量计算提供了准确与可行的计算方法,并有助于得到高精度的反应速率常数,对大分子燃料高精度理论热化学研究具有重要意义.Troubled by the intensified problem of energy and environment,researchers gradually focus on the development of engine performance.The aim of investigating chemical reaction mechanism on combustion is to predict and control the combustion processes for enhancing combustion efficiency,controlling flame stability and reducing emission.Analogy is a way to predict reaction rate constants of large fuel molecules for establishing the combustion reaction model.However,this would cause a large difference compared with the experiments.To better apply large fuel molecule on engine,it is necessary to study high-level chemical kinetics.However,there is a relatively huge computational challenge using prevalent high-level electronic structure method(CCSD(T)/CBS and QCISD(T)/CBS)to deal with the large molecules.Based on the difficulties mentioned above,this paper mainly focused on the current high-level quantum chemistry calculation methods which can be used in large molecule systems,and made a comprehensive introduction of ONIOM[QCISD(T)/CBS:DFT]method.Not only does this method provide an accurately computational and available approach for studying large fuel molecules,also the reliable thermochemical data from the method is useful for the high-level chemical kinetics calculation.

关 键 词：大分子燃料 化学动力学 ONIOM方法 能垒 反应热 

分 类 号：V19[航空宇航科学与技术—人机与环境工程]