Spectroscopy and Dynamics of Radicals and Clusters by Tunable-Laser Dissociative Photodetachment

在这个由化学部实验物理化学计划资助的项目中，Continetti将使用可调谐激光器研究自由基和团簇的解离光剥离（DPD）和光剥离动力学。在这些实验中，光电子-光碎片符合（PPC）光谱结合可调谐激光光剥离/阈值光电子能谱将被用来进行高分辨率的研究，有机自由基以及依赖于波长的DPD动力学的簇阴离子。这些研究将侧重于大气化学中重要的烷氧基自由基的光谱学和离解动力学。电子结构和单分子解离计算将进行，以帮助解释所观察到的能量学和解离动力学。研究团簇阴离子和其他瞬态物种的光剥离动力学的波长依赖性提供了重要的信息，这些系统的电子结构和电子-分子相互作用的问题，是在现代电子结构理论的前沿。该基金支持光谱技术在大气和燃烧化学中重要的短寿命反应分子研究中的应用。研究的一个重要焦点将是一类被称为烷氧基的分子。 它们在城市空气污染化学方面发挥着重要作用，但尽管它们很重要，但关于它们的稳定性和反应的基本信息尚不清楚。该研究项目将有助于填补我们对这些重要物种的理解中的这些空白，为改善大气污染现象的建模提供坚实的经验基础。研究生和本科生将参加涉及最先进的激光和检测技术，计算机建模和化学性质预测的实验。 因此，他们将接受化学研究前沿方法的培训，为深造或进入科学/技术队伍做准备。

In this project funded by the Experimental Physical Chemistry Program of the Chemistry Division, Continetti will use a tunable laser to study the dissociative photodetachment (DPD) and photodetachment dynamics of radicals and clusters. In these experiments, photoelectron-photofragment coincidence (PPC) spectroscopy combined with tunable laser photodetachment/threshold photoelectron spectroscopy will be used to carry out high-resolution studies on organic radicals as well as the wavelength-dependent DPD dynamics of cluster anions. These studies will focus on the spectroscopy and dissociation dynamics of alkoxy radicals important in atmospheric chemistry. Electronic structure and unimolecular dissociation calculations will be carried out to aid in the interpretation of the observed energetics and dissociation dynamics. Studying the wavelength dependence of the photodetachment dynamics of cluster anions and other transient species provides important information on the electronic structure of these systems and problems in electron-molecule interactions that are at the forefront of modern electronic structure theory. This grant supports the application of spectroscopic techniques to the study of short-lived, reactive molecules important in atmospheric and combustion chemistry. An important focus of the research will be on a class of molecules known as alkoxy radicals. They play an important role in aspects of urban air pollution chemistry, but in spite of their importance, basic information about their stability and reactions are not known. This research project will help to fill in these gaps in our understanding of these important species, providing a solid empirical foundation for efforts to improve the modeling of atmospheric pollution phenomena. Graduate and undergraduate students will participate in experiments involving state-of-the-art lasers and detection techniques, computer modeling and prediction of chemical properties. They will thereby receive training in forefront methods of chemical research in preparation for advanced studies or entry into the scientific/technical workforce.