与大气污染相关的活性卤素物种反应机理研究

Reactive halogen species are important components in the atmosphere, which can participate in many air pollution-related chemical processes, play an important role in the climate forcing as well as the atmospheric chemistry which is including composition of the atmosphere, oxidation chemistry, and ozone depletion and so on. Consequently, it is an important frontier research field in the atmospheric chemistry that study on the reaction mechanisms and kinetic behaviors of them deeply. This application intends to do a comprehensive theory research on the radical coupling and photochemical reactions of the reactive halogen species which are related to the air pollutions, using varieties of high-precision quantum chemistry and molecular reaction dynamics calculation methods. Analyze the structure and spectral characteristics of related species, reveal the mechanisms, evolutions and the reaction control factor of the atmospheric chemical reactions of the reactive halogen species, determine the final product states, make the interpretation and judgment for the experimental results, development and improvement the existing kinetic theory and computational procedures, discuss the types of information about the system that is needed in order to estimate the rate constant, explore the applicabity and reliability of the calculation methods for theoretical study on such species, summed up the law, and the research routes would be determined.

活性卤素是大气中的重要物种, 能够参与多种与大气污染相关的化学过程，进而对大气组成，氧化化学，臭氧损耗等大气化学和气候作用力产生重要作用，深入研究活性卤素物种反应机理已成为近年来国际大气化学研究的重要前沿。本申请拟利用多种高精度量子化学和分子反应动力学计算方法，对与大气污染相关的活性卤素物种参与的自由基耦合和光化学反应进行全面的理论计算研究。分析相关物种的结构及光谱特性，揭示活性卤素物种的大气化学反应机制和演变过程及反应的主要控制因子，确定最终产物状态，对已有的实验结果进行解释和判定,发展和改进现有的动力学理论和计算程序，讨论用以预测体系速率常数所需要的信息类型，探索理论研究此类物种计算方法的适用性及可靠性,总结规律，确定理论计算研究路线。

活性卤素物种能够参与大气中众多环境污染物质的化学反应，从而通过海洋，大气和大气气溶胶的化学循环影响大气化学。深入研究活性卤素物种反应机理对于治理环境污染有着重要意义。本项目利用量子化学和分子反应动力学相结合的计算方法对与大气污染相关的活性卤素物种参与的自由基耦合反应进行了详细的理论研究。通过高精度的量子化学计算，获得相关反应的势能面信息，给出了反应物、产物、中间体和过渡态的优化几何、频率和能量，描绘出了可能的反应通道，详细讨论了反应机理。在此基础上，建立合理的动力学模型，从理论上预测了这类多势阱多通道反应的速率常数和产物分支比对压力和温度的依赖关系，得到了主要产物及其分布的详细信息，进而可为此类反应模型的建立提供一些重要的动力学和热力学参数，如反应活化能、指前因子以及反应物和产物标准生成焓等数据，并对已有的实验结果进行解释和判定。本项目的研究成果可为进一步理解、研究与大气污染相关的活性卤素物种的化学反应机理和重要物理过程提供可靠的理论依据，促进更深入的实验研究。