Theoretical and Computational Chemical Dynamics and Energetics

明尼苏达大学的唐纳德·特鲁拉得到了理论和计算化学计划的支持，该计划利用理论和计算化学物理的方法，研究气相中的电子非绝热反应碰撞和非平衡溶剂化对液相反应速率的影响。在电子非绝热反应的处理中，需要强调的问题是：(1)发展精确的量子力学散射理论来计算受耦合势能面支配的体系的态到态反应几率，(2)发展基于改进的退相干和连续表面切换处理的新的半经典方法，(3)针对各种体系的精确的量子力学散射结果检验半经典方法，(4)发展耦合电子波函数和耦合势能面的非绝热表示的新方法，以及(5)利用这些方法来研究可获得实验数据的电子非绝热系统。在非平衡溶剂化效应的处理中，需要注意的问题是：(1)确定广义朗之万溶剂坐标处理溶液中有机反应的适用范围；(2)新方法在二苯甲基氯与溴的反应中的应用。这项研究将影响我们对化学动力学和溶剂化的分子水平的理解，这反过来将对大气和环境化学等领域产生影响。

Donald Truhlar of the University of Minnesota is supported by the Theoretical and Computational Chemistry Program to study electronically nonadiabatic reactive collisions in the gas phase and nonequilibrium solvation effects on liquid phase reaction rates, using methods in theoretical and computational chemical physics. In the treatment of electronically nonadiabatic reactions, issues to be emphasized are: (1) development of accurate quantum mechanical scattering theories to calculate well converged state-to-state reaction probabilities of systems governed by coupled potential energy surfaces, (2) development of new semiclassical methods based on improved treatments of decoherence and continuous surface switching, (3) testing of semiclassical methods against accurate quantum mechanical scattering results for a variety of systems, (4) development of new methods for diabatic representations of coupled electronic wave functions and coupled potential energy surfaces, and (5) use of these methods to study electronically nonadiabatic systems for which experimental data are available. In the treatment of nonequilibrium solvation effects, issues to be emphasized are: (1) delineating the range of applicability of generalized Langevin solvents coordinates for treating organic reactions in solution, and (2) application of new methods to the reactions of diphenylmethyl chloride and bromide. This research will impact our molecular level understanding of chemical dynamics and solvation, which in turn will have implications in areas such as atmospheric and environmental chemistry.