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

北卡罗来纳大学阿什维尔分校的伯特·霍姆斯教授和乔治·希尔德教授在化学结构、动力学和机制计划的支持下，对大气中分子反应路径的动力学和能量学进行了联合实验和计算研究，特别关注将单分子重排作为反应路径的一部分的过程。这项研究建立在PI在识别氢卤烃分子不寻常重排方面的经验基础上，并将这项研究扩大到包括含硫原子的化合物和环丙烷。分子的研究将通过自由基结合的直接合成，以及使用从头算和密度泛函理论的计算建模相结合的方式来研究，重点是表征重排和消除过程的过渡态几何结构。计算项目和实验项目通过使用RRKM理论和直接测量的相对速率常数的比较而相交。该项目的研究成果应该是加深对高层大气中发生的基本过程的理解，以及对焚烧过程中定期释放的化合物的化学的理解。该项目将在每个暑假支持7名本科生进行研究，旨在提高解决问题的技能，并为在高级化学科学领域的职业生涯做准备。

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.