The Interpretation of Processes in Chemical Dynamics Using Chemical and Quantum Nonlinear Phase Spaced Structure

在化学系计算与理论化学项目的资助下，Skodje教授将研究双分子和单分子反应的经典非线性动力学。这项工作处于基础水平，其目标是了解在预测化学反应速率方面具有重要意义的基本动力学效应。经典相空间结构的作用将被强调，反应输运在相空间的性质将被研究使用一个新的理论复杂的衰变率，这是基于奇异吸引子和排斥子理论的最新进展，并给出了一个系统改进的方法来计算速率。这一理论在研究寿命极短的瞬态物质时特别有用，这种物质的寿命与分子内弛豫时间大致相当。将量子相空间流体力学模型应用于多维反应隧穿问题。通过跟踪流体轨道，可以直接找到多维隧道路径。同时，将探讨量子混沌可以看作量子流体动力学中的湍流的概念。最后，将利用量子图的方法探讨分子内振动重分布和反应动力学中的局部化作用。反应性问题的量子图将用于确定定位是否会抑制（或有时促进）化学反应。

With this grant in the Computational and Theoretical Chemistry Program of the Chemistry Division, Professor Skodje will study the classical nonlinear dynamics of bi-molecular and uni-molecular reactions. The work is at a fundamental level with its goal being to understand basic dynamical effects of importance in predicting the rates of chemical reactions. The role of classical phase space structure will be emphasized and the nature of reactive transport in phase space will be investigated using a new theory for complex decay rates, which is based on recent advances in the theory of strange attractors and repellers, and gives a systematically improvable method to calculate rates. The theory will be especially useful in the study of transient species which have extremely short life times, roughly comparable to the intra-molecular relaxation times. A quantum phase space hydrodynamic model will be applied to the problem of multi-dimensional reactive tunneling. The multi-dimensional tunneling path will be found directly by following the fluid orbits. Also, the notion will be explored that quantum chaos can be regarded as turbulence in the quantum fluid dynamics. Finally, the role of localization in intra-molecular vibrational redistribution and in reaction dynamics will be explored by means of quantum maps. Quantum maps for reactive problems will be used to determine whether localization will suppress (or sometimes promote) chemical reaction.