权益分类	功能权益	普通用户	{{item.name}}会员
{{category.name}}	{{benefitItem.name}}

RUI: Microsolvation and halogen substitution effects in weakly bound complexes and carbocations

RUI：弱结合络合物和碳阳离子中的微溶剂化和卤素取代效应

基本信息

批准号：
1664900
负责人：
Robert Chesnut
金额：
$ 22.93万
依托单位：
Eastern Illinois University
依托单位国家：
美国
项目类别：
Continuing Grant
财政年份：
2017
资助国家：
美国
起止时间：
2017-08-01 至 2022-07-31
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=1664900&HistoricalAwards=false
关键词：
RUI Microsolvation halogen substitution effects

项目摘要

In this project, funded by the Chemical Structure, Dynamics and Mechanism A (CSDM-A) program of the Chemistry Division, Professor Sean Peebles and Professor Rebecca Peebles of Eastern Illinois University are using microwave radiation and computational techniques to study how carbon dioxide (CO2) can, under certain conditions, act like a solvent in much the same manner that water can dissolve other molecules and ions. Highly compressed CO2 behaves as a fluid, and is more environmentally friendly and more versatile than many petroleum-derived solvents used in industrial processes. However, the reasons for CO2's versatility are not well understood. In the Peebles' laboratory, a single molecule of solute is isolated with one or a few CO2 solvent molecules. By probing these small clusters with microwave radiation, the arrangement of solvent molecules can be determined. Systematically varying the number of CO2 molecules builds understanding of its unique properties as a solvent. In a second related area of research, electrically charged molecules (carbocations) are generated and their structures are studied via interactions with microwave radiation. As with the CO2 clusters, this provides information about the arrangement of atoms, in this case helping answer questions about the specific steps by which atoms rearrange during a chemical reaction. Both aspects of this research also utilize computational studies to provide more information about the arrangement of electrons within the chemical structures. The results of this research may advance the use of CO2 as a solvent in important chemical processes.The project uses Fourier-transform microwave spectroscopy for investigating structures of unstable chemical species. A theme is the effect of halogen atom substitution within the chemical structures studied. In CO2 microsolvation studies, clusters are generated using a supersonic expansion into a vacuum chamber. Examination of clusters with varying amounts of fluorine substitution builds towards an understanding of why fluorinated species have unusually high solubility in supercritical CO2. Varying the number of CO2 molecules in a cluster allows observation of how weak intermolecular interactions vary as solvation occurs. The knowledge gained from these studies may also help in understanding and building CO2 sequestration frameworks using custom designed molecules. In the second part of the research, carbocations are generated using a pulsed discharge nozzle or electron gun together with the supersonic expansion. Probing with microwave radiation then provides structural information, helping scientists to understand whether carbocations exist in cyclic or noncyclic forms, and how structures change as halogen substitution is varied. In addition to implications for industrial use of CO2, broader impacts are hands-on education of undergraduate students in Chemistry and other STEM fields. Students gain significant practical, problem solving and computer skills and improve their critical thinking abilities.

在这个由化学系化学结构、动力学和机制A（CSDM-A）项目资助的项目中，东伊利诺伊大学的Sean皮布尔斯教授和Rebecca皮布尔斯教授正在使用微波辐射和计算技术研究二氧化碳（CO2）如何在某些条件下像溶剂一样发挥作用，就像水可以溶解其他分子和离子一样。高度压缩的CO2表现为流体，比工业过程中使用的许多石油衍生溶剂更环保，用途更广。然而，二氧化碳的多功能性的原因还没有得到很好的理解。在皮布尔斯的实验室里，单个溶质分子与一个或几个CO2溶剂分子分离。通过用微波辐射探测这些小团簇，可以确定溶剂分子的排列。系统地改变CO2分子的数量有助于理解其作为溶剂的独特性质。在第二个相关的研究领域，产生带电分子（碳正离子），并通过与微波辐射的相互作用研究其结构。与CO2团簇一样，这提供了有关原子排列的信息，在这种情况下，有助于回答有关化学反应中原子重排的具体步骤的问题。这项研究的两个方面还利用计算研究来提供更多关于化学结构中电子排列的信息。这项研究的结果可能会推动在重要的化学过程中使用CO2作为溶剂。该项目使用傅里叶变换微波光谱法研究不稳定化学物质的结构。一个主题是卤素原子取代的化学结构内的影响进行了研究。在CO2微溶剂化研究中，使用超声膨胀到真空室中产生团簇。考察具有不同氟取代量的簇，有助于理解为什么氟化物质在超临界CO2中具有异常高的溶解度。改变团簇中CO2分子的数量可以观察分子间的弱相互作用如何随着溶剂化的发生而变化。从这些研究中获得的知识也可能有助于理解和使用定制设计的分子构建CO2封存框架。在第二部分的研究中，碳正离子产生使用脉冲放电喷嘴或电子枪与超音速膨胀。然后，用微波辐射探测提供结构信息，帮助科学家了解碳正离子是以环状还是非环状形式存在，以及结构如何随着卤素取代的变化而变化。除了对CO2工业使用的影响外，更广泛的影响是对化学和其他STEM领域的本科生进行实践教育。学生获得重要的实践，解决问题和计算机技能，提高他们的批判性思维能力。

项目成果

期刊论文数量（6）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Spectroscopic models of CO2 microsolvation: Bringing data analytics techniques to undergraduate physical chemistry research

CO2 微溶剂化的光谱模型：将数据分析技术引入本科生物理化学研究

DOI：
发表时间：
2021
期刊：
American Chemical Society National Meeting Fall 2021
影响因子：
0
作者：
Peebles, Rebecca A.;Peebles, Sean A.;Kannangara, Prashansa B.;Fino, Hannah L.;Martinez, Melissa A.;Ariyaratne, Tulana
通讯作者：
Ariyaratne, Tulana

Investigation of a polar form of fluoroethylene dimer, (C2H3F)2, by microwave spectroscopy

通过微波光谱研究极性形式的氟乙烯二聚体 (C2H3F)2

DOI：
10.1016/j.molstruc.2020.128038
发表时间：
2020
期刊：
Journal of Molecular Structure
影响因子：
3.8
作者：
Martinez, Melissa A.;West, Channing T.;Pate, Brooks H.;Peebles, Sean A.;Peebles, Rebecca A.
通讯作者：
Peebles, Rebecca A.

Towards and understanding of CO2 microsolvation: Microwave spectroscopy of CO2 complexes with fluoroethylenes

CO2 微溶剂化的走向和理解：CO2 与氟乙烯络合物的微波光谱

DOI：
发表时间：
2017
期刊：
254th American Chemical Society National Meeting
影响因子：
0
作者：
Peebles, Rebecca A.;Peebles, Sean A.;Anderton, Ashley M.;Christenholz, Cori L.;Dorris, Rachel E.;Trendell, William C.
通讯作者：
Trendell, William C.

Microwave Spectra and Structure of Ar–1,3-Difluorobenzene

Ar-1,3-二氟苯的微波光谱和结构

DOI：
10.1021/acs.jpca.8b05282
发表时间：
2018
期刊：
The Journal of Physical Chemistry A
影响因子：
0
作者：
Marshall, Frank E.;Dorris, Rachel;Peebles, Sean A.;Peebles, Rebecca A.;Grubbs, G. S.
通讯作者：
Grubbs, G. S.

σ–Hole activation and structural changes upon perfluorination of aryl halides: direct evidence from gas phase rotational spectroscopy

芳基卤化物全氟化时的空穴活化和结构变化：来自气相旋转光谱的直接证据

DOI：
10.1039/d1cp03023j
发表时间：
2021
期刊：
Physical Chemistry Chemical Physics
影响因子：
3.3
作者：
Lv, Dingding;Maris, Assimo;Evangelisti, Luca;Maggio, Andrea;Song, Wentao;Elliott, Ashley A.;Peebles, Sean A.;Neill, Justin L.;Muckle, Matt T.;Pate, Brooks H.
通讯作者：
Pate, Brooks H.