Nonequilibrium Statistical Mechanics

Peter Wolynes得到了理论和计算化学计划的资助，继续他在非平衡统计力学领域的理论研究。提出的工作集中在气相分子、低温生物分子和团簇中能量流动的新模型，以及生物分子中反应动力学的研究。能流工作是一种分析理论，它借鉴了无序系统中量子传输理论中的技术，并结合了介观方法，研究了随着分子系统的大小增长到接近宏观极限时，分子内动力学是如何变化的。生物反应动力学在很大程度上是计算的，涉及生物分子中的隧道现象，重点是血红素蛋白中的配体重组。第三个研究领域涉及单分子反应动力学的间歇性和微观统计理论，这将有助于解释最近涉及单分子光谱的实验研究。应用统计方法研究处于平衡状态的多粒子系统的物理行为已经很成熟，但类似地应用于非平衡系统，如那些正在进行化学反应的系统，是当前物理化学的一个主要前沿。Wolynes教授正在开发统计技术，以获得关于此类反应系统的有用信息，特别是那些正在进行生物转化或在溶液反应中与溶剂相互作用的系统。

Peter Wolynes is supported by a grant from the Theoretical and Computational Chemistry Program to continue his theoretical research in the area of nonequilibrium statistical mechanics. The proposed work focuses on new models of energy flow in gas phase molecules, biomolecules at low temperatures and clusters, as well as the study of reaction kinetics in biomolecules. The energy flow work is analytical theory using techniques borrowed from the theory of quantum transport in disordered systems combined with a mesoscopic approach that examines how intramolecular dynamics changes as the size of the molecular system grows to approach a macroscopic limit. The biological reaction dynamics is largely computational and deals with tunneling phenomena in biomolecules, focusing on ligand recombination in heme proteins. A third area of study involves intermittency and microscopic theories of statistics of single molecule reaction dynamics which will be useful in interpreting recent experimental studies involving the spectroscopy of single molecules. The application of statistical methods to study the physical behavior of systems containing many particles at equilibrium is well developed, but similar application to nonequilibrium systems such as those undergoing chemical reaction is a major current frontier of physical chemistry. Professor Wolynes is developing statistical techniques to obtain useful information about such reacting systems, particularly those undergoing biological transformations or those interacting with solvents in solution reactions.