Presidential Young Investigator/Path Integral Methods for Molecular Electronic Structure Calculations

David Coker博士得到了理论和计算化学计划授予的总统青年研究人员的支持，以开发许多身体势面的易于计算的描述，这些描述可以准确地描述键的断裂和形成。这些理论势能面对于我们在分子细节水平上进一步理解化学反应是很重要的。科克计划利用多电子交换问题的路径积分公式与描述环状聚合物分子之间经典缔合平衡的宏配分函数之间的同构，作为处理分子价电子关联运动的一种方法。科克建议使用几种新的加权技术来绕过与这种方法相关的已知相位问题，以处理反对称多电子波函数。这项研究的长期目标是计算许多体势能面，这些势能面允许电子分布随核运动动态变化，从而提供目前大多数方法所缺乏的高精度，用于化学反应体系的分子动力学模拟。

Dr. David Coker is supported by a Presidential Young Investigator Grant from the Theoretical and Computational Chemistry Program to develop computationally tractable descriptions of many body potential surfaces which can accurately describe bond breakage and formation. These theoretical potential energy surfaces are important in furthering our understanding of chemical reactions at the molecular level of detail. Coker plans to exploit the isomorphism between the path integral formulation for the many electon exchange problem, and the grand partition function describing the classical association equilibrium between cyclic polymer molecules as a method for dealing with correlated motions of molecular valence electrons. Coker proposes the use of several novel weighting techniques to circumvent the known phase problems associated with this methodology in treating antisymmetric many electron wavefunctions. The long term goal of this research is the calculation of many body potential energy surfaces which allow the electronic distribution to vary dynamically with the nuclear motion, and therefore provide a high level of accuracy currently missing from most approches to molecular dynamic simulations of chemically reacting systems.