Molecular Structure and Dynamics Beyond the Born-Oppenheimer Approximation

超越玻恩-奥本海默近似的分子结构和动力学

• 批准号: 9701480
• 负责人: Edward Grant
• 金额: $ 43.92万
• 依托单位: Purdue Research Foundation
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1997
• 资助国家: 美国
• 起止时间: 1997-05-01 至 2000-04-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9701480&HistoricalAwards=false
• 关键词: Molecular; Structure; Dynamics; Beyond; Born

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.

普渡大学的爱德华·格兰特在实验物理化学项目的支持下，继续他对小分子高激发态下的状态间光电离和分子内弛豫动力学的研究。 这项工作的主要目标是为许多多原子系统积累足够分辨率的详细状态光谱信息，以支持全面的多通道量子缺陷理论计算。 Systems to be studied include hydrocarbon and metal-centered free radicals that form closed-shell cations. PI将使用多共振激发技术对与电离和解离连续体耦合的状态跃迁相关的共振线形和能量进行高分辨率光谱测量，并使用专门的检测方法进行光选择来研究阳离子和前体自由基的电子基态中的振动结构。 描述孤立分子中的能量流的努力极大地增进了我们对化学反应性的理解，并且多年来一直是化学物理学研究的重要焦点。 如今，分子内弛豫的研究仍然是实验和理论分子动力学之间的重要联系点。 特别重要的是电子自由度和核间自由度之间的能量转移。 这些过程的详细动态可能会产生重大的化学后果。 例如，与电子坐标和核间能量之间的能量转移动力学相关的问题是当代指导化学转化结果的努力的基础。