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

该提案将使用2009年美国复苏和再投资法案（公法111-5）提供的资金进行奖励，并符合2009年3月20日白宫备忘录第2节中规定的要求，该备忘录题为“确保复苏法案资金的负责任支出”。我还确认，作为认知项目官员，该提案不支持恢复法案A部分第1604节中描述的项目。马里兰州大学的米勒德亚历山大得到了理论化学和计算计划的EAGER奖的支持，该计划旨在对复杂化学系统中多个势能表面的化学动力学研究的先进方法进行探索性研究。许多有趣的化学都涉及自由基，即电子壳层未填满的分子。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--电子各向异性--所以完整的描述涉及不止一个势能面。该研究涉及确定相互作用势，正确描述开壳层原子和分子自由基与扩展系统之间的相互作用，以及如何通过与最近邻溶剂分子的相互作用来修改小分子解离和小自由基重组。亚历山大正在探索将量子和经典速率理论扩展到涉及多个电子状态的情况的方法。这涉及到扩展系统的基于路径积分的量子描述，以包括每个不同电子状态的完整位置（或动量）状态集。这项研究在许多重要的技术领域，包括燃烧，材料加工，等离子体和修复化学具有潜在的影响。

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.