重要小分子的光解离和光电离微观动力学  

The Photodissociation and Photoionization Dynamics of Some Important Small Molecules

作　　者：程敏 张丽娟 徐西玲[1,3] 高蕻 郑卫军 Min Cheng;Lijuan Zhang;Xiling Xu;Hong Gao;Weijun Zheng(Institute of Chemistry,Chinese Academy of Sciences,Beijing 100190,China;Shangdong University of Aeronautics,Binzhou 256600,China;University of Chinese Academy of Sciences,Beijing 100049,China)

机构地区：[1]中国科学院化学研究所,北京100190 [2]山东航空学院,滨州256600 [3]中国科学院大学,北京100049

出　　处：《化学进展》2024年第12期1830-1848,共19页Progress in Chemistry

基　　金：国家自然科学基金委员会;科技部;中国科学院;中国科学院化学研究所;北京分子科学国家研究中心。

摘　　要：小分子光解离和光电离的微观反应机理研究,是分子反应动力学研究领域的核心和焦点之一,具有重要的理论意义和应用价值。它不仅可揭示分子与光相互作用的物理化学本质,还有助于从量子层次认识化学反应并最终调控化学反应过程。本文系统回顾了朱起鹤院士团队多年来在该领域取得的研究成果。他们利用自主研制的多台分子光解碎片平动能谱仪,通过测量光解碎片的平动能分布和空间角分布,深入研究了一系列卤代烃在A带的光解动力学特性,揭示了其光解规律和微观反应机理。利用自行搭建的共振增强多光子电离和质量解析阈值电离光谱仪,结合量子化学计算,他们系统研究了一系列苯衍生物在不同电子态的几何构型、振动光谱、跃迁能和电离能等,总结了多卤素效应、取代基效应、构象异构效应等对分子性质及其光谱的影响规律,为揭示分子激发态、离子态的特性提供了重要信息。这些研究不仅深化了对化学反应微观机理的理解,还为大气化学、环境化学、生物化学和材料科学等领域的实际应用提供了重要的理论依据。The study of microscopic mechanisms of photodissociation and photoionization on small molecules is the major focus in the field of molecular reaction dynamics,which is important from both theoretical and practical aspects.It not only can reveal the physicochemical nature of the interaction between molecules and light,but also can help to understand and eventually regulate the chemical reaction process at the quantum level.This paper systematically reviews the research accomplishments achieved by Academician Zhu Qihe’s group in this field over the years.By utilizing the home-made photofragment translational spectrometers,they have comprehensively explored the photodissociation processes and revealed the microscopic reaction mechanisms for a series of halogenated hydrocarbons in the A band,by measuring the translational energies and spatial angular distributions of the photofragments.They have also investigated the geometric configurations,vibrational spectra,transition energies and ionization energies of benzene derivatives in different electronic states,by using the home-made resonance-enhanced multi-photon ionization and mass-analyzed threshold ionization spectrometers combined with quantum chemical calculations.They summarized the influences of multi-halogen effects,substituent effects and conformational isomerism effects on molecular properties and spectroscopy,supplying important information on the characteristics of excited and ionic states of molecules.These achievements not only deepen our understanding of the microscopic mechanism of chemical reactions,but also provide an important theoretical basis for their practical applications in the fields of atmospheric chemistry,environmental chemistry,biochemistry and material sciences.

关 键 词：光解离 光电离 卤代烃 苯衍生物 

分 类 号：O644.1[理学—物理化学]