Theoretical and Computational Chemical Dynamics and Energetics

唐纳德·特鲁拉得到了理论和计算化学计划的资助，继续他在化学动力学和能量学方面的工作。提出了三个方面的研究：1)改进了分析和预测光化学反应的理论框架；2)发展了处理凝聚相化学反应中量子动力学效应的改进方法；3)改进了处理小团簇性质和动力学的量子力学方法。这项研究的主要目标包括：1)分析电子非绝热化学反应的轨道表面跳跃算法的准确性，通过将它们与他的新的线性代数变分方法产生的收敛的量子动力学结果进行对比来测试它们；2)找出轨道表面跳跃方法的具体特征，并利用这一知识来集中未来的努力来改进方法；3)开发一个类似过渡态理论的总体猝灭速率常数的近似；4)更好地理解决定通过漏斗的激基络合物分解的分支率的物理效应；5)将量子力学效应引入到实际的变分过渡态理论计算中；6)进一步发展稳定化方法，作为多维共振的实用工具；7)开发并行计算机，对四体系统进行有效的量子力学计算；8)利用对氟化氢二聚体的精确量子动力学计算，作为改善该系统势能面的手段。特鲁拉的研究旨在对化学动力学和溶剂化有一个基本的分子水平的理解。这项研究在大气和环境化学领域具有重要的战略意义。

Donald Truhlar is supported by a grant from the Theoretical and Computational Chemistry Program to continue his work on chemical dynamics and energetics. Three areas of research are proposed: 1) development of an improved theoretical framework for the analysis and prediction of photochemical reactions; 2) development of improved methods for treating quantum dynamical effects in condensed-phase chemical reactions; and 3) improved methods for the quantum mechanical treatment of the properties and dynamics of small clusters. Major objectives of the research include: 1) To analyze the accuracy of trajectory surface hopping algorithms for electronically nonadiabatic chemical reactions by testing them against converged quantum dynamical results to be produced by his new linear algebraic variational methods; 2) To pinpoint the specific features of trajectory surface hopping methods that are most responsible for any observed inaccuracies and to use this knowledge to focus future efforts to improve the methods; 3) To develop a transition-state-theory-like approximation for overall quenching rate constants; 4) To better understand the physical effects that determine branching ratios for decomposition of exciplexes through funnels; 5) To incorporate quantum mechanical effects into practical variational transition state theory calculations; 6) To further develop the stabilization method as a practical tool for multi-dimensional resonances; 7) To exploit parallel computers for efficient quantum mechanical calculations on four-body systems; and 8) To use the accurate quantum dynamical calculations on hydrogen fluoride dimer as a means of improving the potential energy surface for this system. Truhlar's research is aimed at a basic molecular level understanding of chemical dynamics and solvation. This research has important strategic implications in areas of atmospheric and environmental chemistry.