Active Control of Chemical Reactions

化学反应的主动控制

• 批准号: 0131001
• 负责人: Stuart Rice
• 金额: $ 43.2万
• 依托单位: University of Chicago
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2001
• 资助国家: 美国
• 起止时间: 2001-12-15 至 2005-11-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0131001&HistoricalAwards=false
• 关键词: Active; Control; Chemical; Reactions

In this award funded by the Theoretical and Computational Chemistry Program of the Chemistry Division, Rice will study the theory for the active control of the evolution of quantum many-body systems in order to establish conditions under which active control of a unimolecular reaction can be achieved in a dense liquid phase. The principal focus in these investigations will be on developing new variants of methods that use coherent excitation of states with or without adiabatic transfer of population. A main focus in on the development of new stimulated Raman adiabatic passage (STIRAP) laser excitation schemes for both gas phase and solution phase reactions. Other promising methods as well as refinements and extensions of previous implementations of active control of molecular dynamics will also be studied.Selective control of product formation in a chemical reaction has been sought persistently throughout the evolution of chemistry. Using such control of a reaction would allow one to generate a particular product mostly or completely. Control has been accomplished at the macroscopic level by manipulating external factors such as temperature, pressure, solvent character, etc. With the advent of the tunable laser, it was hoped that product selectivity could be controlled at the microscopic level, and that individual bonds within a molecule could be selectively broken. It was very quickly found that energy absorbed by a molecule was not easily localized in individual bonds, but preferred to redistribute throughout the molecule. More recently, however, the concept of laser selective chemistry has had a rebirth, and theories developed by Rice and others have shown that energy could be localized by carefully choosing a complex sequence of laser pulses of prescribed shapes. If this theory can be put to practice experimentally, it will be possible to realize the goal of microscopic selective control of chemical reactions.

在这个由化学部理论和计算化学计划资助的奖项中，赖斯将研究量子多体系统演化的主动控制理论，以建立在稠密液相中实现单分子反应主动控制的条件。 在这些调查的主要重点将是开发新的变种的方法，使用相干激发态或没有绝热转移的人口。 主要研究了气相和液相反应的新型受激拉曼绝热通道（STIRAP）激光激发方案。 其他有前途的方法，以及改进和扩展以前的实施主动控制的分子dynamics.Selective控制在化学反应中的产品形成一直在寻求持续的化学的发展。 使用这样的反应控制将允许人们大部分或完全地产生特定产物。 控制已经完成了在宏观层面上通过操纵外部因素，如温度，压力，溶剂特性等，随着可调谐激光器的出现，人们希望，产品的选择性可以控制在微观层面上，和一个分子内的各个键可以选择性地打破。 人们很快发现，分子吸收的能量不容易局限在单个键中，而是倾向于在整个分子中重新分布。 然而，最近，激光选择性化学的概念已经重生，赖斯和其他人发展的理论表明，通过仔细选择具有规定形状的激光脉冲的复杂序列，能量可以被局部化。 如果这一理论能在实验上得到应用，就有可能实现化学反应的微观选择性控制。