Vibrational Control of Bimolecular Reactions in Gases and Liquids

气体和液体中双分子反应的振动控制

• 批准号: 9632997
• 负责人: F. Fleming Crim
• 金额: $ 51.1万
• 依托单位: University of Wisconsin-Madison
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 1996
• 资助国家: 美国
• 起止时间: 1996-08-01 至 2000-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9632997&HistoricalAwards=false
• 关键词: Vibrational; Control; Bimolecular; Reactions; Gases

In this project in the Experimental Physical Chemistry Program of the Chemistry Division, Crim will continue studies of the influence of vibrational excitation on the course and rate of bimolecular chemical reactions. The current work will extend the investigations from the gas into the liquid phase in the expectation of demonstrating selective control of the course of a bimolecular reaction by preferentially breaking a chosen bond. In the proposed gas-phase studies visible or infrared photons will excite vibrations of bonds which then react with photolytically created atoms to form products. Measuring the quantum states of the products helps identify the pathways of the reactions accelerated by the vibrational excitation. In favorable cases, one can cleave a bond preferentially. Vibrationally driven bimolecular reactions in liquids and supercritical fluids require ultrafast excitation of reagents and detection of products. Nonlinear light generation will provide the excitation and absorption or coherent Raman scattering will be used for detection. Collaborations with a theoretician will allow tests of dynamical theories and potential energy surface calculations. In this research the outcome of a chemical reaction between a polyatomic molecule and an atom is directly controlled by exciting the molecular vibration of the bond which is expected to break in the course of the reaction. This expectation is based on the fact that the geometry change that occurs in going from reactants to products first requires the stretching of bonds similar to that which occurs during molecular vibrations. The results of this research are expected to have an impact in atmospheric chemistry, combustion, and the understanding of plasmas

在这个项目中，在实验物理化学计划的 化学部，犯罪将继续研究的影响， 振动激发对双分子化学过程和速率的影响 反应. 目前的工作将把调查从气体 在液相中，期望展示选择性 控制双分子反应的过程， 打破一个选择的债券。 在拟议的气相研究中， 红外光子将激发键的振动， 光解产生的原子形成产物。 测量量子 产物的状态有助于确定反应的途径 被振动激发加速。 在有利的情况下，可以 优先切断键。 振动驱动双分子反应 在液体和超临界流体中需要超快激发 试剂和产品检测。 非线性光产生将 提供激发和吸收或相干拉曼散射 用于检测。 与理论家的合作 动力学理论和势能面计算的测试。 在这项研究中，多原子之间的化学反应的结果 分子和原子是通过激发分子直接控制的 振动的债券，预计将打破的过程中， 反应 这种期望是基于几何形状发生变化的事实 从反应物到生成物的过程中， 类似于在分子过程中发生的键的拉伸 震动 这项研究的结果有望产生影响 在大气化学、燃烧和对等离子体的理解方面