Gas Phase Oxidation of Resonance-Stabilized Radicals

在这个项目中，由化学部的化学结构，动力学和机制B计划和NSF EPSCoR资助，西弗吉尼亚大学化学系的Fabien Goulay教授研究了燃烧反应机制。中心焦点是可以在燃烧环境中积累的大而稳定的自由基的氧化。 已知这些中间体在多环芳烃（PAH）和颗粒物等污染物的形成过程中起主要作用。气相和高温反应的实验和计算研究。实验研究采用光谱方法来表征中间体及其化学行为。这项研究提供了有关反应机制的关键信息，这些信息将用于开发更有效的运输和发电燃烧过程。该项目还为本科生和研究生提供培训机会，包括第一代大学生和阿巴拉契亚地区的学生，他们在科学领域的代表性历来不足。该项目研究了气相中共振稳定自由基的氧化。这些自由基可以建立在可观的浓度，最近被假设为多环芳烃和烟灰的前体。这些自由基在气相中的浓度主要通过与非常活泼的物种（例如羟基自由基）的氧化反应而耗尽。虽然已经进行了理论研究来预测它们对羟基自由基的反应性，但没有实验数据来验证这些预测。自由基-自由基反应的实验研究是困难的，因为两种自由基需要在足够的浓度下同时形成。Goulay教授和他的团队使用激光光解在流动反应器中产生两种自由基，并使用激光光谱和质谱检测它们的浓度。理论计算被用来分析反应机理。这项工作也有助于未来的科学家的职业发展，通过提供最先进的实验资源，包括同步加速器设施的培训。这个奖项反映了NSF的法定使命，并已被认为是值得支持的评估使用基金会的智力价值和更广泛的影响审查标准。

In this project, funded by the Chemical Structure, Dynamics and Mechanisms B Program of the Chemistry Division and by NSF EPSCoR, Professor Fabien Goulay from the Department of Chemistry at West Virginia University investigates combustion reaction mechanisms. The central focus is on the oxidation of large, stable free radicals which can accumulate in combustion environments. These intermediates are known to play a major role during the formation of pollutants such as polycyclic aromatic hydrocarbons (PAHs) and particulate matter. Gas phase and high temperature reactions are investigated both experimentally and computationally. Experimental studies employ spectroscopic methods to characterize intermediates and their chemical behavior. This research provides critical information on reaction mechanisms that will be used to develop more efficient combustion processes for transportation and power generation. This project also provides training opportunities for undergraduate and graduate students, including first generation college students and students from the Appalachian region, who have been traditionally underrepresented in the sciences. The project investigates the oxidation of resonance-stabilized radicals in the gas phase. These radicals can build up in appreciable concentrations and have recently been hypothesized as precursors to polycyclic aromatic hydrocarbons and soot. The concentration of these radicals in the gas phase is depleted mostly by oxidation reactions with very reactive species, such as the hydroxyl radical. Although theoretical studies have been performed to predict their reactivity toward the hydroxyl radicals, no experimental data are available to validate these predictions. The experimental study of radical - radical reactions is difficult because both radicals need to be formed simultaneously at sufficient concentrations. Professor Goulay and his Group produce both radicals in a flow reactor using laser photolysis, and detect their concentrations using laser spectroscopy and mass spectrometry. Theoretical calculations are used to analyze the reaction mechanisms. This work also contributes to the career development of future scientists by providing training at state-of-the-art experimental resources, including synchrotron facilities.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.