Gas Phase Oxidation of Resonance-Stabilized Radicals

在这个由化学分部化学结构、动力学和机理B项目和NSF EPSCoR资助的项目中，来自西弗吉尼亚大学化学系的Fabien Goulay教授研究了燃烧反应机制。中心焦点是氧化大，稳定的自由基，可以积累在燃烧环境。已知这些中间体在多环芳烃（PAHs）和颗粒物等污染物的形成过程中起主要作用。对气相反应和高温反应进行了实验和计算研究。实验研究采用光谱方法来表征中间体及其化学行为。这项研究提供了关于反应机制的关键信息，这些信息将用于开发更有效的燃烧过程，用于运输和发电。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来自阿巴拉契亚地区的学生，他们传统上在科学领域的代表性不足。该项目研究了气相中共振稳定自由基的氧化。这些自由基可以以可观的浓度积累，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是通过与非常活跃的物质（如羟基自由基）的氧化反应而消耗的。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，因为两个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这两种自由基，并使用激光光谱和质谱法检测它们的浓度。用理论计算分析了反应机理。这项工作还有助于未来科学家的职业发展，提供最先进的实验资源，包括同步加速器设施的培训。该奖项反映了美国国家科学基金会的法定使命，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 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.