Theory of Chemical Dynamics

加州大学伯克利分校的威廉·米勒得到了理论和计算化学计划的资助，继续他在理论气相化学动力学方面的研究。他将开发用于计算反应速率常数的严格量子方法和用于模拟复杂动力学过程的半经典方法。量子方法将使用直接技术来产生速率常数，而不需要所有的状态到状态的细节。米勒还将发展半经典的初值表示方法，作为一种潜在的普遍的分子动力学方法，包括量子效应、隧道效应和电子非绝热效应。这些新方法的新应用也将被执行，例如在亚乙叉/乙炔重排中的共振隧穿。这项研究的目标是发展能够提供对化学动力学的定量描述的理论概念和方法，这是一种类似于电子结构理论的从头算量子化学的从头算化学动力学。这项研究针对的是最基本的化学水平，即两个相互碰撞的分子在气相中发生的化学反应。这一非常基本但高度复杂的过程是理论可以严格应用到的最简单的化学反应，并构成了理解所有其他更复杂的化学过程的基础。

William Miller, University of California Berkeley, is supported by a grant from the Theoretical and Computational Chemistry Program to continue his research on theoretical gas-phase chemical dynamics. He will develop rigorous quantum methods for reaction rate constant calculations and semiclassical methods for simulations of complex dynamical processes. The quantum methodology will employ direct techniques that result in rate constants without all of the state-to-state details. Miller also will develop the semiclassical initial-value-representation method as a potentially universal treatment of molecular dynamics, including quantum effects, tunneling, and electronically non-adiabatic effects. Novel applications of these new methods will also be performed, e.g., resonance tunneling in the vinylidene/acetylene rearrangement. The goal of this research is to develop the theoretical concepts and methodologies that can provide a quantitative description of chemical dynamics, a kind of ab initio chemical dynamics akin to the ab initio quantum chemistry of electronic structure theory. This research is directed at the most fundamental level of chemistry, i.e., the chemical reaction taking place in the gas phase between two colliding molecules. This very basic, yet highly complex, process is the simplest chemical reaction to which theory can be rigorously applied, and forms the basis for understanding all other more complex chemical processes.