Molecular Structure and Dynamics Beyond the Born-Oppenheimer Approximation

普渡大学的爱德华·格兰特是由实验性的 物理化学计划，继续他的研究，国家对国家 分子内弛豫动力学 小分子的激发态 这项工作的主要目标是 积累，对于一些多原子系统，状态详细 足够分辨率的光谱信息，以支持全尺寸 多通道量子亏损理论计算。 待研究系统 包括烃和金属中心自由基，其形成 闭壳层阳离子 PI将使用多共振激励 技术，使高分辨率光谱测量的共振 与过渡状态相关的线形和能量， 耦合到电离和解离连续体，和光选择， 专门的检测方法来研究振转结构的 阳离子和前体自由基的电子基态。 描述孤立分子中能量流的努力增加了 对我们理解化学反应性有很大的帮助， 多年来一直是化学物理研究的重点。 的 分子内弛豫的研究至今仍是 实验分子动力学和理论分子动力学之间的联系 特别 重要的是电子和核间的能量转移 自由度。 这些过程的详细动力学可以给出 会产生严重的化学后果。 例如， 与电子之间能量转移的动力学有关 协调和核间的协调是当代努力的基础， 化学转化的结果。

Edward Grant of Purdue University is supported by the Experimental Physical Chemistry Program to continue his research on state-to-state photoionization and dynamics of intramolecular relaxation in highly excited states of small molecules. The main objective of this work is to accumulate, for a number of polyatomic systems, state-detailed spectroscopic information of sufficient resolution to support full-scale Multichannel Quantum Defect Theory calculations. Systems to be studied include hydrocarbon and metal-centered free radicals that form closed-shell cations. The PI will use multiresonant excitation techniques to make high-resolution spectroscopic measurements of resonant lineshapes and energies associated with transitions to states which are coupled to ionization and dissociation continua, and photoselection with specialized detection methods to study rovibrational structure in the electronic ground states of cations and precursor free radicals. The effort to describe energy flow in isolated molecules has added considerably to our understanding of chemical reactivity, and served for many years as an important focus of research in chemical physics. The study of intramolecular relaxation remains today a vital point of contact between experimental and theoretical molecular dynamics. Particularly important is the transfer of energy between electronic and internuclear degrees of freedom. The detailed dynamics of such processes can give rise to significant chemical consequences. For example, issues associated with the dynamics of energy transfer between electronic coordinates and internuclear ones underlie contemporary efforts to direct the outcomes of chemical transformations.