Theoretical Descriptions of Vibrational Energy Transfer in Gas and Liquid Phases

气相和液相振动能量传递的理论描述

• 批准号: 0076128
• 负责人: Edwin Sibert
• 金额: $ 27万
• 依托单位: University of Wisconsin-Madison
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2000
• 资助国家: 美国
• 起止时间: 2000-07-01 至 2003-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0076128&HistoricalAwards=false
• 关键词: Theoretical; Descriptions; Vibrational; Energy; Transfer

Ned Sibert of the University of Wisconsin, Madison, is supported by the Theoretical and Computational Chemistry Program to investigate theoretically energy flow in polyatomic molecules in both gas and liquid phases, using combined classical and quantum techniques. The primary goal of this effort is to develop molecular models of the dynamics that are consistent with experimental observations. This work will highlight and elucidate the mechanisms by which a system returns to equilibrium, and permit the sorting out of quantum from classical effects in relaxation processes. Research topics include the calculation of rotation-vibration spectra of methane and its deuterated analogs using perturbative techniques developed by the PI, the detailed study of gas phase relaxation of carbon disulfide and ultimately more complex systems via collisions, and the theoretical study of energy flow in the condensed phase. A quantitative analysis of the dynamics in these problems involves the accurate treatment of both the molecular eigenstates and their interactions with the surrounding environment. The research outcomes are expected to lead to an improved understanding of the competing pathways of energy flow in medium-size molecules and of the coupling terms that are responsible for these pathways. Successful modeling of atmospheric phenomena, combustion chemistry, and drug design via molecular simulations require accurate knowledge of the forces between the atoms and molecules. Recent experimental advances in ultrafast laser spectroscopy have enabled scientists to probe the time evolution of vibrationally excited systems to determine the pathways of energy flow in molecules. Outcomes from theoretical and experimental studies of vibrational energy transfer reveal potentially important information about the forces that control the above technologically important processes.

威斯康星大学麦迪逊分校的NED Sibert得到了理论和计算化学计划的支持，该计划使用经典和量子技术合并，研究气体和液相的多原子分子中的理论能量流。 这项工作的主要目的是开发与实验观察一致的动力学的分子模型。 这项工作将突出并阐明系统返回平衡的机制，并允许在弛豫过程中从经典效应中排序量子。 研究主题包括使用PI开发的扰动技术计算甲烷的旋转振动光谱及其剥离的类似物，对二硫化物碳二硫化物和最终更复杂系统的气相松弛的详细研究以及凝聚相的能量流的理论研究。 对这些问题中动力学的定量分析涉及对分子本征态及其与周围环境的相互作用的准确处理。 预计研究结果将导致对中等大小分子和负责这些途径的耦合术语的能量流的竞争途径的了解。通过分子模拟的大气现象，燃烧化学和药物设计的成功建模需要准确了解原子和分子之间的力。 超快激光光谱法的最新实验进步使科学家能够探测振动激发系统的时间演变，以确定分子中能流的途径。 从振动能量转移的理论和实验研究中得出的结果揭示了有关控制上述技术重要过程的力的潜在重要信息。