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.

有了这个续期奖，有机和高分子化学项目继续支持康奈尔大学化学系巴里·卡彭特教授的工作。这项研究将扩展PI对有机反应中非统计动力学的研究。在很大程度上，由于卡彭特教授的工作，人们最近认识到，有机化学中的许多活性中间体是通过对其可用振动模式的选择性激发而形成的。如果这些中间体以比振动能量重新分配更快的速度进入产物，反应并不总是沿着最低能量路径进行，并导致意想不到的产物。在这项提案中，将进行旨在合成和研究可能导致能量以非统计方式分布的额外活性中间体的分子的实验。这项将现代计算化学与复杂实验相结合的工作的一个主要重点将是那些位于深能量极小值的中间体，以及非统计动力学对它们的反应性的作用。该项目的第二个主题是扩大可以探索非统计动力学问题的反应范围。这些效应主要是针对热产生的单重态双自由基提出的。在新的工作中，这些想法将扩展到光化学，卡宾化学，以及化学激活的稳定分子的化学。该项目的总体目标是更新化学动力学模型，以考虑动态效应。由于化学动力学在生物学、大气和环境化学、燃烧以及其他许多领域都起着至关重要的作用，因此提高动力学模型的精度有望产生广泛的影响。此外，作为这项研究的参与者，学生将接受高度跨学科的培训，这将有助于提供现代科学研究现在所需的专业知识。