RUI: Condensed-Phase Effects on the Structural and Energetic Properties of Nitrogen Donor - SOx Complexes

RUI：凝聚相对氮供体 - SOx 复合物结构和能量特性的影响

• 批准号: 2154736
• 负责人: James Phillips
• 金额: $ 31.33万
• 依托单位: University of Wisconsin-Eau Claire
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2022
• 资助国家: 美国
• 起止时间: 2022-09-01 至 2025-08-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2154736&HistoricalAwards=false
• 关键词: RUI; Condensed; Phase; Effects; Structural

In this project funded by the Chemical Structure, Dynamics and Mechanisms-A program of the Chemistry Division, Professor James Phillips and his undergraduate researchers at the University of Wisconsin-Eau Claire will study how the structures of certain stable molecules change as a result of their associations with each other. Molecular structure is typically unaffected by chemical environment; distances between atoms typically do not change when a substance condenses or goes into solution. However, certain “molecular complexes” - associations of two or more otherwise stable molecules - can undergo major changes of this ilk, but the overall generality of such effects is not well-established. This project will characterize a series of complexes apt to change structure in inert, non-interacting “solvent” environments known as “cryogenic matrices” (solid samples of argon, neon, or nitrogen, frozen at temperatures near absolute zero). The complexes will be studied by probing their resonant frequencies (how fast or easily their chemical bonds vibrate), which shift systematically when structural changes occur. In addition, the systems will be explored by computer simulations of the bonding to address the underlying factors that drive the unusual structural changes. The knowledge gained from these studies will contribute to a fundamental understanding of the nature of chemical bonding, which in turn can help other researchers to better understand and predict chemical reactivity in the research lab, industrial settings, and the environment. The project will take place at an accessible, public comprehensive university (UW-Eau Claire), and will provide transformative research, mentoring, and career development experiences for undergraduate students. This combined quantum-chemical and experimental (matrix-IR and UV spectroscopic) investigation will target three types of systems: i) H3N–SO2 and its methylated analogs, ii) Pyridine - SO2, and its fluoropyridine analogs, and, iii) the analogous SO3 complexes. The central hypothesis is that bonds about the central S-atom in SOx will manifest repulsive forces that impede further coordination, and lead to extreme structural changes in inert media. Confirmation of this will manifest a refined understanding of factors affecting coordinate bond strength, which may impact many areas of chemistry.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.

在这个由化学部化学结构、动力学和机理项目资助的项目中，詹姆斯·菲利普斯教授和他在威斯康星大学欧克莱尔分校的本科生研究人员将研究某些稳定分子的结构如何因其相互关联而发生变化。 分子结构通常不受化学环境影响；当物质凝结或进入溶液时，原子之间的距离通常不会改变。然而，某些“分子复合物”——两个或多个稳定分子的结合——可能会发生类似的重大变化，但这种效应的总体普遍性尚未得到充分证实。该项目将表征一系列易于在惰性、非相互作用的“溶剂”环境中改变结构的复合物，称为“低温基质”（氩、氖或氮的固体样品，在接近绝对零的温度下冷冻）。这些复合物将通过探测它们的共振频率（化学键振动的速度或容易程度）来研究，当结构发生变化时，共振频率会系统地变化。此外，还将通过计算机模拟粘合来探索这些系统，以解决驱动异常结构变化的潜在因素。从这些研究中获得的知识将有助于对化学键本质的基本理解，进而可以帮助其他研究人员更好地理解和预测研究实验室、工业环境和环境中的化学反应性。 该项目将在一所交通便利的公立综合性大学（威斯康星大学欧克莱尔分校）进行，将为本科生提供变革性的研究、指导和职业发展经验。这种量子化学和实验（基质红外和紫外光谱）相结合的研究将针对三种类型的系统：i) H3N-SO2 及其甲基化类似物，ii) 吡啶 - SO2 及其氟吡啶类似物，以及 iii) 类似的 SO3 复合物。中心假设是，SOx 中中心 S 原子周围的键会表现出排斥力，阻碍进一步的协调，并导致惰性介质中的极端结构变化。对此的确认将体现出对影响配位键强度的因素的深入理解，这可能会影响化学的许多领域。该奖项反映了 NSF 的法定使命，并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，被认为值得支持。