Linear and Nonlinear Spectroscopy of Unimolecular Dynamics

单分子动力学的线性和非线性光谱

• 批准号: 9975428
• 负责人: Patrick Vaccaro
• 金额: $ 59.1万
• 依托单位: Yale University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1999
• 资助国家: 美国
• 起止时间: 1999-08-15 至 2005-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9975428&HistoricalAwards=false
• 关键词: Linear; Nonlinear; Spectroscopy; Unimolecular; Dynamics

In this project supported by the Experimental Physical Chemistry Program of the Chemistry Division, Patrick Vaccaro of Yale University will study the unimolecular reaction dynamics of several small to medium-sized molecules using a variety of linear and nonlinear spectroscopic techniques. Earlier work on unimolecular transformations in S2O and on intramolecular hydrogen bonding and proton transfer in malonaldehyde will be extended, the structure unimolecular transformations in the cyanogen family will be examined in detail, and transformations between isomers in the cyanogen family, CNNC, CNCN, and CNNC will be studied. Experimental findings will be compared to calculations using new theoretical methods. Various degenerate four-wave mixing (DFWM) techniques will be developed and quantified, including Cavity Ring-Down Spectroscopy (CRDS). The proposed activities will advance the knowledge and the understanding of unimolecular dynamics and the interpretation of signals derived from linear and nonlinear optical measurements. The investigations undertaken in this project will help increase understanding of molecular behavior that plays a basic and important role in a variety of chemical and biological processes. For example, the sequence of bond reorganization events that occur during chemical syntheses can be elucidated, allowing chemists to devise more efficient routes to a desired product. The knowledge of structural preferences of molecules with bonds that can freely rotate impacts the understanding of protein folding in molecules of biological importance.

在这个由化学系实验物理化学项目支持的项目中，耶鲁大学的帕特里克·瓦卡罗（Patrick Vaccaro）将使用各种线性和非线性光谱技术研究几种中小分子的单分子反应动力学。 将扩展前期关于S2O单分子转化和丙二醛分子内氢键和质子转移的工作，详细研究氰族结构单分子转化，研究氰族异构体之间、CNNC、CNCN和CNNC之间的转化。 实验结果将与使用新理论方法的计算进行比较。 将开发和量化各种简并四波混频（DFWM）技术，包括腔衰荡光谱（CRDS）。 拟议的活动将增进对单分子动力学的知识和理解以及对线性和非线性光学测量信号的解释。 该项目中进行的研究将有助于增进对在各种化学和生物过程中发挥基本和重要作用的分子行为的理解。 例如，可以阐明化学合成过程中发生的键重组事件的顺序，从而使化学家能够设计出更有效的路线来获得所需的产物。 了解具有可自由旋转键的分子的结构偏好会影响对具有生物学重要性的分子中蛋白质折叠的理解。