Path integral and semiclassical approaches to the dynamics of large chemical systems

南希·马克里是由理论和计算化学计划资助的支持，继续她对大型化学系统动力学的路径积分和半经典方法的理论研究。 Makri将使用影响泛函方法来研究复杂多原子环境中系统的量子动力学。 她将利用的影响功能，允许配对的前向和反向时间演化算子的结构。 这导致服从蒙特卡罗积分的表达式。 两个程序将被调查：1）一个局部二次，瞬时正常模式展开的溶剂势;和2）一个严格的半经典的向前向后的初始值表示的影响功能。 Makri计划对团簇和流体中的能量转移动力学进行基准计算和应用。化学家感兴趣的大多数反应都发生在溶剂存在的凝聚相系统中。 处理这种复杂系统的理论模型仍处于发展的早期阶段。 Makri正在开发新的理论方法，用于处理溶剂化化学系统进行化学反应，其中量子效应很重要。

Nancy Makri is supported by a grant from the Theoretical and Computational Chemistry Program to continue her theoretical research on path integral and semiclassical approaches to the dynamics of large chemical systems. Makri will use an influence functional approach to study the quantum dynamics of a system in a complex polyatomic environment. She will exploit the structure of the influence functional that allows pairing of the forward and reverse time evolution operators. This leads to expressions amenable to Monte Carlo integration. Two procedures will be investigated: 1) a locally quadratic, instantaneous normal mode expansion of the solvent potential; and 2) a rigorous semiclassical forward-backward initial value representation of the influence functional. Makri plans to conduct benchmark calculations and applications to the dynamics of energy transfer in clusters and fluids.The large majority of reactions that are of interest to chemists occur in condensed phase systems in the presence of solvent. The theoretical models for treating such complex systems are still in the early stage of development. Makri is developing new theoretical approaches for dealing with solvated chemical systems undergoing chemical reactions where quantum effects are important.