Theoretical Studies of Excited State Reaction Dynamics, Surface Chemistry, and Condensed Phase Processes

波士顿大学的大卫科克得到了理论和计算化学项目的资助，对激发态反应动力学、表面化学和凝聚相过程进行理论研究。 理论方法解决一类化学问题，其中有很强的电子和振动自由度之间的混合。在这些情况下，更常见的绝热近似是不够的。 Coker使用他的新方法来计算实时相关函数，该方法基于传播子的半经典表达式。 这种方法能够一致地处理核和电子自由度，并为处理生化和环境意义的问题以及解决溶剂在基本化学过程中的作用提供了可能性。许多工业，生化和环境化学反应涉及多个能量表面，这是由于不同的电子构型。 在平流层中，一个含氯的分子在被中和成氯化氢分子之前可以降解许多臭氧分子。 了解哪些含氯分子容易光解为活性ClO，将有助于减轻臭氧消耗。 这些反应属于化学反应的范畴，可以使用本基金开发的方法进行研究。

David Coker, of Boston University, is supported by a grant from the Theoretical and Computational Chemistry Program to perform theoretical studies of excited state reaction dynamics, surface chemistry and condensed-phase processes. The theoretical methods address a class of chemical problems in which there is strong mixing between the electronic and vibrational degrees of freedom. In these instances, the more common adiabatic approximation is insufficient. Coker uses his new method for computing real-time correlation functions, which is based on semi-classical expressions for the propagator. This approach enables a consistent treatment of nuclear and electronic degrees of freedom and opens up the possibility for treating problems of biochemical and environmental significance and to address the role of the solvent on fundamental chemical processes.Many industrial, biochemical and environmental chemical reactions involve multiple energy surfaces, which are due to different electronic configurations. In the stratosphere a single-chlorine containing molecule can degrade numerous ozone molecules before it is neutralized into a hydrogen-chloride molecule. Understanding which chlorine-containing molecules are easily photolyzed to reactive ClO containing species will aid in alleviating ozone depletion. Such reactions reside in the class of chemical reactions amenable to study using the methods developed under this grant.