Organic Chemistry in Harsh Reaction Environments

在这个由化学学部化学结构、动力学和机理b项目资助的项目中，威斯康星大学麦迪逊分校化学系的Robert J. McMahon教授研究了有机化合物在极端温度、压力或辐射条件下的行为。这些条件类似于火焰（燃烧）或太空中的条件，导致有机化合物的降解并产生高度反应产物的复杂混合物。这个项目探索这些活性分子的性质和化学反应。这项研究为理解两个截然不同的问题提供了基础——一个涉及燃烧，另一个涉及空间化学。有机燃料的燃烧是我国能源供应和国民经济的核心。对燃烧的基本理解提供了提高燃料燃烧的能源效率和减少不完全燃烧产生的污染物（烟灰）的可能性。在星际空间中，我们现在知道，数百种不同的有机化合物存在于整个星系的环境中，这些环境非常恶劣，因为它们太热了（靠近恒星），或者因为它们太冷了（远离恒星）。研究这些环境是理解宇宙中有机物质分布和识别可能成为生命前身的分子的关键一步。作为跨学科研究团队的一部分，该研究项目支持研究生和本科生在复杂化学问题研究方面的教育。机械有机化学的培训为随后在工业界或学术界的职业生涯提供了宝贵的基础。麦克马洪教授和他的学生从事各种科学教育和推广活动。该建议解决了机械有机化学中的挑战，这些挑战与我们对恶劣反应环境的理解有关。目前的提案沿着三个主要方向发展这些问题：1)通过旋转光谱产生，检测和表征关键化学靶点，2)碳链分子的光谱和光化学，以及3)有机化学中的量子力学隧道。拟议研究的科学影响超出了化学范畴，并跨越了当代科学的各个领域。自旋离域和自旋极化的研究是开发具有新型电学和磁学性能的新型有机材料的基础。对活性有机物质的研究有助于对燃烧的基本理解。阿塔卡马大型毫米波阵列（ALMA），一个由美国国家科学基金会资助的位于智利北部的射电望远镜天文干涉仪，正在产生大量新的射电天文数据。这些数据只能通过与本项目中获得的实验室光谱进行比较来解释。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 Mechanism-B Program of the Chemistry Division, Professor Robert J. McMahon of the Department of Chemistry at the University of Wisconsin-Madison investigates the behavior of organic compounds under extreme conditions of temperature, pressure, or radiation. These conditions, which are similar to the conditions found in flames (combustion) or in space, cause the degradation of organic compounds and generate a complex mixture of highly reactive products. This project explores the properties and chemical reactions of these reactive molecules. This research provides a foundation for understanding two very different problems – one involving combustion and another involving the chemistry of space. Combustion of organic fuels is central to our nation’s energy supply and national economy. A fundamental understanding of combustion offers the possibility of enhancing the energy efficiency of fuel combustion and minimizing pollutants (soot) that arise from incomplete combustion. In interstellar space, it is now known that hundreds of different organic compounds exist throughout the galaxy in environments that are harsh because they are so hot (near stars) or because they are so cold (far from stars). Studying these environments is a crucial step in understanding the distribution of organic material in the universe and identifying molecules that could be precursors to life. This research program supports the education of graduate and undergraduate students in the study of complex chemical problems as part of an interdisciplinary research team. Training in mechanistic organic chemistry provides a valuable foundation for subsequent careers in industry or academia. Professor McMahon and his student engage in a variety of science education and outreach activities.This proposal addresses challenges in mechanistic organic chemistry that are relevant to our understanding of harsh reaction environments. The current proposal develops these issues along three major lines: 1) generation, detection, and characterization of key chemical targets by rotational spectroscopy, 2) spectroscopy and photochemistry of carbon-chain molecules, and 3) quantum mechanical tunneling in organic chemistry. The scientific impact of the proposed research reaches beyond chemistry and cuts across diverse areas of contemporary science. Studies of spin delocalization and spin polarization underpin the development of new organic materials with novel electrical and magnetic properties. Studies of reactive organic species contribute to a fundamental understanding of combustion. The Atacama Large Millimeter Array (ALMA), an NSF-funded astronomical interferometer of radio telescopes in northern Chile, is generating a deluge of new radio-astronomical data. These data can be interpreted only by comparison with laboratory spectra of the type that are obtained in this project.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.