EAGER: Development of new methods for the study of chemical dynamics on multiple potential energy surfaces in complex chemical systems

这项提案将使用2009年《美国复苏和再投资法案》(公法111-5)提供的资金授予，并符合2009年3月20日题为《确保负责任地使用复苏法案资金》的白宫备忘录第2节规定的要求。作为认知项目官员，我还申明，该提案不支持复苏法案A部分1604节中描述的项目，马里兰大学的米勒德·亚历山大得到了理论化学和计算项目的热切支持，该项目旨在对研究复杂化学体系中多个势能面的化学动力学的先进方法进行探索性研究。许多有趣的化学涉及自由基，即具有未填充电子壳层的分子。因此，一个自由基与另一个原子或分子的相互作用具有电子方向性，即电子各向异性，因此完整的描述涉及不止一个势能面。研究内容包括用扩展体系确定正确描述开壳原子与分子自由基间相互作用的相互作用势，以及小分子解离和小自由基复合如何通过与最近邻溶剂分子的相互作用来修饰。Alexander正在探索将量子和经典速率理论扩展到涉及不止一个电子态的情况下的方法。这包括扩展基于路径积分的系统量子描述，以包括每个不同电子态的位置(或动量)状态的全集。这项研究在燃烧、材料加工、等离子体和修复化学等许多重要技术领域具有潜在的影响。

This proposal will be awarded using funds made available by the American Recovery and Reinvestment Act of 2009 (Public Law 111-5), and meets the requirements established in Section 2 of the White House Memorandum entitled, Ensuring Responsible Spending of Recovery Act Funds, dated March 20, 2009. I also affirm, as the cognizant Program Officer, that the proposal does not support projects described in Section 1604 of Division A of the Recovery ActMillard Alexander of the University of Maryland is supported by an EAGER award from the Theoretical Chemistry and Computational program to conduct exploratory research on advanced methods for the study of chemical dynamics of multiple potential energy surfaces in complex chemical systems. Much interesting chemistry involves radicals, molecules with unfilled electronic shells. The interaction of a radical with another atom or molecule has, therefore, an electronic directionality - an electronic anisotropy - so that the complete description involves more than one potential energy surface. The research involves the determination of interaction potentials that describe correctly the interactions between open-shell atomic and molecular radicals with extended systems, and how small-molecule dissociation and small radical recombination are modified by interactions with nearest-neighbor solvent molecules. Alexander is exploring methods to extend quantum and classical rate theory to situations where more than one electronic state is involved. This involves extending a path-integral based quantum description of the system to include a full set of position (or momentum) states for each different electronic state. This research has potential impact in many technological important areas including combustion, materials processing, plasmas and remediation chemistry.