Theoretical Studies of State to State Chemistry

西北大学的George Schatz得到理论和计算化学计划的支持，开发新的理论方法来描述在气相中发生的化学反应的动力学。该项目的总体目标是改进计算方法，为涉及原子和小分子(最多6个原子)的反应的可测量性质提供定量描述。将探索三个相互关联的研究主题。首先，将描述由于系间交叉而导致的自旋禁忌过程是重要的反应。其次，将表征试剂振动激发对反应速率常数的影响，特别强调确定需要哪种试剂激发才能实现最有效的反应速度提高。第三，将探索生成用于模拟反应过程的全局解析势面的方法。研究成果有望有助于描述大气和燃烧化学中重要的化学反应，此外还将在描述激光化学和分子束实验中得到应用。气相中的化学反应动力学仍然是基础研究的一个充满活力的领域。该项目在大气和燃烧化学方面有相关的应用，并在理论和实验之间提供了一个富有成效的会合点。最终，这项研究的成果将蔓延到其他领域，包括液体动力学、生物分子模拟、气体表面动力学和材料化学。

George Schatz of Northwestern University is supported by the Theoretical and Computational Chemistry Program to develop new theoretical methods for describing the dynamics of chemical reactions that take place in the gas phase. The overall project goal is to advance computational methods that provide a quantitative description of measurable properties of reactions involving atoms and small molecules (up to 6 atoms). Three interconnected research topics will be explored. First, reactions where spin-forbidden processes due to intersystem crossing are important will be described. Second, the effect of reagent vibrational excitation on the rate constants for reaction will be characterized, with particular emphasis on determining what kinds of reagent excitation are needed in order to achieve the most efficient reaction rates enhancements. Third, approaches for generating global analytical potential surfaces for simulating reactive processes will be explored. Research outcomes are expected to be useful for characterizing chemical reactions that are important in atmospheric and combustion chemistry, and in addition will find applications in describing laser chemistry and molecular beam experiments. The dynamics of chemical reactions in the gas phase continues to be a vibrant area of basic research. This project has relevant applications to atmospheric and combustion chemistry, as well as providing a fruitful meeting ground between theory and experiment. Ultimately, the outcomes of this research will spill over into other fields, including dynamics in liquids, biomolecular simulation, gas-surface dynamics, and materials chemistry.