RUI: Characterizing Pyrolysis and Combustion Pathways for Asphaltene Model Compounds

在该项目中，由化学部的化学结构，动力学机制B计划资助，里士满大学化学系的Carol教区教授正在探索在油页岩中发现的分子的高温分解机制，油页岩是一种替代燃料来源。 该项目位于物理化学，有机化学，物理学和计算机科学的接口，非常适合各级科学家的教育。该教区实验室是特别有利的位置，提供教育和培训的学生在科学代表性不足的最高水平。本科和学士后学生将学习应用严格的量子化学方法来表征重要的能量相关的化学反应。这些研究的结果将提供基本信息，以支持以能源为基础的经济，并直接解决油页岩工业的重要问题;即油页岩和油砂的分子成分的高温分解和氧化的潜在分子机制。更具体地，该项目支持对沥青质中发现的分子的高温分解和燃烧途径的计算研究，以及表征所产生的多自由基中间体。沥青质是北美尚未开发的烃类燃料来源;然而，关于这些沉积物的分子性质的信息最近才变得可用，并且对这些物质的反应途径、燃烧效率和反应性知之甚少。 在该项目中，单一参比方法被用于研究以下反应途径：1）萘化合物的燃烧和热解，2）可能导致沥青质稠合芳族核的富电子炔部分的电环化，以及3）辛基苯炔中的氢转移过程。 多参比方法被用于研究1）沿着这些反应途径产生的多自由基中间体，例如萘和烷基萘自由基以及蒽双自由基，2）杂芳族双自由基的电子耦合和电子激发光谱，这将有助于这些物种的实验表征，3）已知在噻吩的热解中产生的线性和二乙烯基硫烷双自由基，和4）涉及四自由基的反应和通过-该奖项反映了NSF的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

In this project, funded by the Chemical Structure, Dynamics & Mechanism B Program of the Chemistry Division, Professor Carol Parish of the Chemistry Department at the University of Richmond is exploring the high temperature decomposition mechanisms of the molecules found in oil shale, an alternative fuel source. The project lies at the interface of physical chemistry, organic chemistry, physics and computer science, and is well suited to the education of scientists at all levels. The Parish laboratory is particularly well-positioned to provide the highest level of education and training for students underrepresented in science. Undergraduate and post-baccalaureate students will learn to apply rigorous quantum chemical methods to the characterization of important energy-related chemical reactions. The results from these studies will provide fundamental information to support an energy-based economy and directly address important problems in the oil shale industry; namely, the underlying molecular mechanisms for high temperature decomposition and oxidation of the molecular constituents of oil shale and oil sands.More specifically, this project supports computational investigations of the high temperature decomposition and combustion pathways for molecules found in asphaltenes, as well as to characterize the polyradical intermediates that are produced. Asphaltenes represent an untapped source of hydrocarbon fuel in North America; however, information about the molecular nature of these deposits has only recently become available and very little is known about the reaction pathways, combustion efficiency and reactivity of these species. In this project, single reference methods are being used to study reaction pathways for 1) combustion and pyrolysis of naphthalenic compounds, 2) electrocyclizations of electron-rich acetylenic moieties that may lead to asphaltene fused aromatic cores and 3) hydrogen transfer processes in octylbenzyne. Multi-reference methods are being used to study 1) polyradical intermediates produced along those reaction pathways such as naphthalene and alkyl naphthalene radicals and the anthracene diradicals, 2) electron coupling and electronic excitation spectra for heteroaromatic diradicals that will aid in the experimental characterization of these species, 3) linear and divinylsulfane diradicals known to be produced in the pyrolysis of thiophene and 4) reactions involving tetraradicals and the role that through-bond coupling plays in radical electron interaction.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.