NSF Award
1800014
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.<br/><br/>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.<br/><br/>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.
