RUI: Experimental and Computational Study of Unimolecular Gas-phase Rearrangements

RUI：单分子气相重排的实验和计算研究

基本信息

批准号：
1111546
负责人：
Bert Holmes
金额：
$ 29.1万
依托单位：
University of North Carolina at Asheville
依托单位国家：
美国
项目类别：
Continuing Grant
财政年份：
2011
资助国家：
美国
起止时间：
2011-09-15 至 2016-08-31
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=1111546&HistoricalAwards=false
关键词：
RUI Experimental Computational Study Unimolecular

项目摘要

Professors Bert Holmes and George Heard of the University of North Carolina Asheville are supported by the Chemical Structure, Dynamics and Mechanisms Program to carry out a joint experimental and computational study of the kinetics and energetics of reaction pathways of molecules in the atmosphere, with particular attention to processes involving a unimolecular rearrangement as a part of the reaction pathway. This research builds on the PIs' experience in identifying unusual rearrangements of hydrohalocarbon molecules, and expands that study to include compounds containing sulfur atoms as well as cyclopropanes. Molecules will be studied by a combination of direct synthesis from radical combination, and computational modeling using ab initio and density functional theory with a focus on characterizing transition state geometries for rearrangement and elimination processes. Computational and experimental projects intersect by the comparison of relative rate constants using RRKM theory and direct measurement.Research outcomes from this project should be an increased understanding of fundamental processes going on in the upper atmosphere and an understanding of the chemistry of compounds released regularly in incineration processes. This project will support seven undergraduate students per summer in research that is intended to improve problem-solving skills and provide preparation for a career in advanced chemical sciences.

伯特·福尔摩斯（Bert Holmes）教授和乔治教授听说了北卡罗来纳大学阿什维尔大学（University of North Carolina Asheville）的支持，由化学结构，动力学和机制计划提供支持，以对大气中分子中分子反应路径的动力学和能量学进行联合实验和计算研究，并特别注意涉及涉及涉及该反应的一部分反应途径的过程。这项研究基于PIS在识别水力碳分子异常重排方面的经验，并扩展了该研究，以包括含有硫原子的化合物以及环丙烷。分子将通过从自由基组合的直接合成以及使用从头算和密度功能理论进行计算建模的组合，重点是表征过渡状态几何形状以进行重排和消除过程。通过使用RRKM理论和直接测量的相对速率常数进行比较，计算和实验项目的研究应越来越多地了解对高层大气中发生的基本过程的理解以及对在incineration过程中定期发布的化合物化学的理解。该项目将为每个夏天的七个本科生提供研究，旨在提高解决问题的技能，并为高级化学科学的职业提供准备。