RUI: Spectroscopic Characterization and Low Temperature Kinetic Study of Hydrogenated Aromatic Radicals

RUI：氢化芳香族自由基的光谱表征和低温动力学研究

• 批准号: 2348916
• 负责人: Jay Amicangelo
• 金额: $ 33万
• 依托单位: Pennsylvania State Univ University Park
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2024
• 资助国家: 美国
• 起止时间: 2024-06-01 至 2027-05-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2348916&HistoricalAwards=false
• 关键词: RUI; Spectroscopic; Characterization; Low; Temperature

With support from the Chemical Structure, Dynamics, and Mechanisms A (CSDM-A) program in the Division of Chemistry, Professor Jay Amicangelo of Pennsylvania State University-Erie is investigating the infrared spectra and formation kinetics of hydrogenated radicals produced by the reactions of hydrogen atoms with monosubstituted benzene rings using matrix isolation infrared spectroscopy and computational chemistry. Hydrogenated aromatic radicals are thought to be important intermediates in different chemical processes such as pyrolysis, combustion, hydrogenation, and hydrogenolysis. Complete understanding of the nature of these species as possible intermediates in various important chemical processes remains elusive because of the scarcity of the experimental infrared spectra and formation kinetics data of the hydrogenated radicals at low temperatures. Professor Amicangelo and his students will utilize a microwave discharge source with an appropriate precursor molecule and co-deposit the hydrogen atoms with the ring molecules in argon matrices to obtain the infrared spectra of the hydrogenated radicals and conduct the kinetic studies. Their studies could extend the number of hydrogenated radicals characterized by infrared spectroscopy and provide new low temperature data on their formation kinetics. The Amicangelo research group will also engage in an outreach component to visit high school chemistry classes within the Erie School District with portable scientific devices to help the chemistry teachers give their students access to hands-on, high quality scientific laboratory experiments.This proposal focuses on characterizing the infrared spectra and studying the kinetics of hydrogenated radicals formed by the reaction of hydrogen atoms with monosubstituted benzene rings (C6H5X, X = OCH3, CH3, Cl, CN) using matrix isolation infrared spectroscopy and quantum chemical calculations. Hydrogenated radicals of aromatic rings are thought to be important intermediates in several different important chemical processes, such as pyrolysis, combustion, hydrogenation, and hydrogenolysis. Characterizing the infrared spectra of the hydrogenated radicals will be accomplished by using a microwave discharge source with an appropriate precursor molecule and co-depositing the hydrogen atoms with the ring molecules in 15 K argon matrices. Studying the kinetics of the hydrogenated radicals will involve trapping the hydrogen atoms in the argon matrices at 10 K, followed by monitoring the radical growth kinetics as the hydrogen atoms react with the ring molecules in the argon matrices in the 14 – 20 K temperature range. The IR spectra of these transient intermediates will provide highly valuable windows into the mechanisms of important transformations of aromatic substrates, and as such, will be of broad value to the synthetic, mechanistic and computational chemistry communities.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.

在化学系化学结构，动力学和机制A（CSDM-A）计划的支持下，宾夕法尼亚州立大学伊利分校的Jay Amicangelo教授正在研究氢原子与单取代苯环反应产生的氢化自由基的红外光谱和形成动力学，使用基质隔离红外光谱和计算化学。氢化芳族自由基被认为是不同化学过程如热解、燃烧、氢化和氢解中的重要中间体。由于缺乏低温下氢化自由基的红外光谱和形成动力学实验数据，对这些物种作为各种重要化学过程中可能的中间体的性质的完全理解仍然是难以捉摸的。Amicangelo教授和他的学生将利用带有适当前体分子的微波放电源，将氢原子与环分子共同沉积在氩气基质中，以获得氢化自由基的红外光谱并进行动力学研究。他们的研究可以扩展红外光谱表征的氢化自由基的数量，并提供有关其形成动力学的新的低温数据。Amicangelo研究小组还将参与一个外展部分，用便携式科学设备访问伊利学区内的高中化学课，帮助化学教师让学生动手，高质量的科学实验室实验。该提案的重点是表征红外光谱和研究氢原子与单取代苯反应形成的氢化自由基的动力学环（C6 H5 X，X = OCH 3，CH 3，Cl，CN）的结构。芳香环的氢化自由基被认为是几种不同的重要化学过程中的重要中间体，例如热解、燃烧、氢化和氢解。表征的氢化自由基的红外光谱将通过使用微波放电源与适当的前体分子和共沉积的氢原子与环分子在15 K氩矩阵。研究氢化自由基的动力学将涉及在10 K下将氢原子捕获在氩基质中，然后在14 - 20 K温度范围内监测氢原子与氩基质中的环分子反应时的自由基生长动力学。这些瞬态中间体的红外光谱将提供非常有价值的窗口到芳香族底物的重要转化机制，因此，将具有广泛的价值，合成，机械和计算化学community.This奖项反映了NSF的法定使命，并已被认为是值得通过使用基金会的智力价值和更广泛的影响审查标准进行评估的支持。