Organic Chemistry in Harsh Reaction Environments

恶劣反应环境下的有机化学

• 批准号: 2245738
• 负责人: Robert McMahon
• 金额: $ 63万
• 依托单位: University of Wisconsin-Madison
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2023
• 资助国家: 美国
• 起止时间: 2023-07-01 至 2026-06-30
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2245738&HistoricalAwards=false
• 关键词: Organic; Chemistry; Harsh; Reaction; Environments

With support of the Chemical Structure, Dynamics & Mechanism-B (CSDM-B) Program of the Chemistry Division, Professor Robert J. McMahon of the Department of Chemistry at the University of Wisconsin-Madison will investigate the behavior of organic compounds under harsh 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. The proposed research will explore the chemical 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. The proposed program benefits society by supporting 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.The proposed research will explore the structure, reactivity, and spectroscopy of carbon-rich reactive intermediates. The data obtained in these studies will provide a foundation for understanding the chemistry of organic matter in harsh environments. These studies impact diverse areas of chemical and physical science, including astrochemistry, flames and combustion, and soot formation. The program will address fundamental questions concerning the chemical nature of what is now recognized to be the dominant reservoir of organic compounds in the universe. The determination of accurate equilibrium structures will provide important benchmarks for prototypical organic molecules, and theory can be further used to establish thermodynamic parameters that are important for modeling combustion chemistry. Studies of quantum mechanical tunneling reactions are of fundamental interest in mechanistic chemistry and are inherently relevant to chemical processes occurring in cold environments – including interstellar clouds, planets, moons, small solar system bodies, and comets. The proposed research melds state-of-the-art techniques in both theory and experiment to address complex problems.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、动力学和机理B(CSDM-B)计划的支持下，威斯康星大学麦迪逊分校化学系的罗伯特·J·麦克马洪教授将研究有机化合物在严酷的温度、压力或辐射条件下的行为。这些条件类似于火焰(燃烧)或空间中的条件，会导致有机化合物的降解，并产生高活性产物的复杂混合物。这项拟议的研究将探索这些活性分子的化学性质和化学反应。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。有机燃料的燃烧关系到我国的能源供应和国民经济。对燃烧的基本了解提供了提高燃料燃烧的能源效率和将不完全燃烧产生的污染物(烟尘)降至最低的可能性。在星际空间，人们现在知道，数百种不同的有机化合物存在于整个银河系的恶劣环境中，因为它们太热了(靠近恒星)，或者因为它们太冷了(远离恒星)。研究这些环境是了解有机物质在宇宙中的分布和识别可能是生命先驱的分子的关键一步。作为跨学科研究团队的一部分，拟议的计划通过支持研究生和本科生研究复杂化学问题的教育而造福于社会。机械有机化学方面的培训为随后的工业或学术生涯提供了宝贵的基础。拟议的研究将探索富碳活性中间体的结构、反应活性和光谱。这些研究中获得的数据将为理解恶劣环境中有机物的化学组成提供基础。这些研究影响了化学和物理科学的各个领域，包括天体化学、火焰和燃烧以及煤烟形成。该计划将解决与目前公认的宇宙中占主导地位的有机化合物储存库的化学性质有关的基本问题。准确的平衡结构的确定将为原型有机分子提供重要的基准，理论可以进一步用于建立对燃烧化学建模重要的热力学参数。对量子力学隧穿反应的研究是机械化学中的基本兴趣，与发生在寒冷环境中的化学过程有着内在的联系--包括星际云、行星、卫星、小型太阳系天体和彗星。这项拟议的研究融合了最先进的理论和实验技术，以解决复杂的问题。这一奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。

项目成果

The 130 – 750 GHz rotational spectrum of 2-cyanopyridine – Analysis of the ground vibrational state and the Coriolis-coupled dyad of its lowest-energy fundamental states

2-氰基吡啶的 130 × 750 GHz 旋转光谱 — 基振动态及其最低能量基本态的科里奥利耦合二元组分析

• DOI: 10.1016/j.jms.2023.111842
• 发表时间: 2023
• 期刊: Journal of Molecular Spectroscopy
• 影响因子: 1.4
• 作者: Dorman, P. Matisha;Esselman, Brian J.;Zdanovskaia, Maria A.;Woods, R. Claude;McMahon, Robert J.
• 通讯作者: McMahon, Robert J.

Precise Equilibrium Structure of Benzene

苯的精确平衡结构

• DOI: 10.1021/jacs.3c03109
• 发表时间: 2023
• 期刊: Journal of the American Chemical Society
• 影响因子: 15
• 作者: Esselman, Brian J.;Zdanovskaia, Maria A.;Owen, Andrew N.;Stanton, John F.;Woods, R. Claude;McMahon, Robert J.
• 通讯作者: McMahon, Robert J.

Ketene Lamp

乙烯酮灯

• 发表时间: 2023
• 期刊: Fusion
• 作者: Wood, Samuel;Drier, Tracy;Woods, R. Claude;McMahon, Robert J.
• 通讯作者: McMahon, Robert J.

Rotational Spectroscopy of 1-Cyano-2-methylenecyclopropane (C 5 H 5 N)─A Newly Synthesized Pyridine Isomer

1-氰基-2-亚甲基环丙烷 (C 5 H 5 N)——一种新合成的吡啶异构体的旋转光谱

• DOI: 10.1021/acs.jpca.3c08002
• 发表时间: 2024
• 期刊: The Journal of Physical Chemistry A
• 作者: Jean, Dairen R.;Wood, Samuel A.;Esselman, Brian J.;Woods, R. Claude;McMahon, Robert J.
• 通讯作者: McMahon, Robert J.

The 235–360 GHz Rotational Spectrum of 1-Oxaspiro[2.5]octa-4,7-dien-6-one─Analysis of the Ground Vibrational State and Its 10 Lowest-Energy Vibrationally Excited States

1-Oxspiro[2.5]octa-4,7-dien-6-one 的 235～360 GHz 旋转频谱——地面振动状态及其 10 个最低能量振动激发状态的分析

• DOI: 10.1021/acs.jpca.3c07049
• 发表时间: 2024
• 期刊: The Journal of Physical Chemistry A
• 作者: Esselman, Brian J.;Pimentel, Edward B.;Styers, William H.;Jean, Dairen R.;Woods, R. Claude;McMahon, Robert J.
• 通讯作者: McMahon, Robert J.