Nonstatistical Dynamics of Reactive Intermediates

反应中间体的非统计动力学

• 批准号: 0516991
• 负责人: David Collum
• 金额: --
• 依托单位: Cornell University
• 依托单位国家: 美国
• 项目类别: Continuing grant
• 财政年份: 2005
• 资助国家: 美国
• 起止时间: 2005-08-01 至 2008-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0516991&HistoricalAwards=false
• 关键词: Nonstatistical; Dynamics; Reactive; Intermediates

With this renewal award, the Organic and Macromolecular Chemistry Program continues its support of the work of Professor Barry Carpenter of the Department of Chemistry at Cornell University. The research will extend the PI's studies of nonstatistical dynamics in organic reactions. Largely as a result of Professor Carpenter's work it has recently been recognized that many reactive intermediates in organic chemistry are formed with selective excitation of their available vibrational modes. If these intermediates go on to products faster than they undergo vibrational energy redistribution, the reaction does not always follow the lowest energy path and leads to unexpected products. In this proposal, experiments designed to synthesize and investigate molecules that may lead to additional reactive intermediates in which the energy is distributed in a nonstatistical manner will be carried out. One principal focus of the work, which combines modern computational chemistry with sophisticated experiments, will be on those intermediates lying in deep energy minima and the role of nonstatistical dynamics on their reactivity. A second theme of the project is to broaden the range of reactions in which issues of nonstatistical dynamics can be explored. Primarily, these effects have been proposed for thermally generated singlet biradicals. In the new work, the ideas will be extended to photochemistry, to carbene chemistry, and to the chemistry of chemically activated stable molecules.A general goal of the project is to update models of chemical kinetics to take account of dynamic effects. Since chemical kinetics plays vital roles in biology, atmospheric and environmental chemistry, combustion, and in a variety of other domains, improving the accuracy of kinetic models is expected to have wide-ranging impact. In addition, the highly interdisciplinary training that students will receive as participants in this research will help provide the expertise that modern scientific research now demands.

有了这个更新奖，有机和大分子化学项目继续支持康奈尔大学化学系Barry Carpenter教授的工作。这项研究将扩展PI对有机反应非统计动力学的研究。主要由于卡彭特教授的工作，最近人们认识到，有机化学中的许多反应性中间体是在其可用振动模式的选择性激发下形成的。如果这些中间体生成产物的速度比它们经历振动能量重新分配的速度快，则反应并不总是遵循最低能量路径，从而产生意想不到的产物。在这个提议中，实验旨在合成和研究可能导致额外的反应中间体的分子，其中能量以非统计方式分布。这项工作将现代计算化学与复杂的实验相结合，其主要重点将放在那些处于深能量极小值的中间体以及非统计动力学对其反应性的作用上。该项目的第二个主题是扩大非统计动力学问题可以探索的反应范围。这些效应主要是针对热生成的单线态双自由基提出的。在新的工作中，这些思想将扩展到光化学、碳化学和化学活化稳定分子的化学。该项目的总体目标是更新化学动力学模型，以考虑动力学效应。由于化学动力学在生物学、大气和环境化学、燃烧以及许多其他领域起着至关重要的作用，因此提高动力学模型的准确性有望产生广泛的影响。此外，学生作为这项研究的参与者将接受高度跨学科的训练，这将有助于提供现代科学研究所需要的专业知识。