CAS: Collaborative Research: Photophysics and Electron Transfer Reactivity of Ion Radical Excited States

CAS：合作研究：离子自由基激发态的光物理学和电子转移反应性

• 批准号: 2246509
• 负责人: Aimee Tomlinson
• 金额: $ 17.86万
• 依托单位: University of North Georgia
• 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: 2023-06-01 至 2026-05-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2246509&HistoricalAwards=false
• 关键词: CAS; Collaborative; Research; Photophysics; Electron

With support of the Chemical Structure, Dynamics & Mechanisms-B (CSDM-B) Program of the Chemistry Division, Professor Kirk S. Schanze of the Department of Chemistry at the University of Texas at San Antonio, and Professor Aimée Tomlinson of the Department of Chemistry at the University of North Georgia are studying the properties of charged organic radicals with useful properties as photosensitizers for organic reactions and solar energy conversion. The project lies at the interface of organic, physical, and computational chemistry and is well suited for broad education of chemical scientists at all levels. The investigators will leverage the diverse populations at their respective universities to engage underrepresented students in all aspects of the research. This collaboration will provide engaged research students access to the feedback loop between theory and experiment thus enriching their chemical research projects.This project seeks to provide an understanding of the factors that control ion radical doublet excited states and their electron transfer reactivity, through a collaborative approach involving experimental photophysics and computational chemistry using density functional theory and time dependent density functional theory. Stable anion and cation radicals of a variety of molecules will be prepared by chemical reduction or oxidation followed by characterization of their photophysical properties through picosecond transient absorption and fluorescence spectroscopy methods. Key parameters to be determined include the lifetime and energy of the doublet excited state, along with the radiative and non-radiative decay rate constants. The experimental results will be utilized to inform structure-property relationships for the ion radical doublet excited states, with specific aim to delineate whether an energy gap law correlation exists between their energy and non-radiative decay rate. Theory will be used to identify molecular systems that are optimized with respect to doublet excited state energy and lifetime thereby, guiding the design of optimized electron transfer photosensitizers.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、动力学机制-B（CSDM-B）项目的支持下，德克萨斯大学圣安东尼奥分校化学系的尚泽和北格鲁吉亚大学化学系的Aimée Tomlinson教授正在研究带电有机自由基的性质，这些自由基具有作为有机反应和太阳能转换的光敏剂的有用性质。 该项目位于有机，物理和计算化学的接口，非常适合各级化学科学家的广泛教育。研究人员将利用各自大学的不同人群，让代表性不足的学生参与研究的各个方面。 该合作将为从事研究的学生提供理论和实验之间的反馈回路，从而丰富他们的化学研究项目。该项目旨在通过使用密度泛函理论和时间依赖密度泛函理论的实验电子物理学和计算化学的合作方法，了解控制离子自由基双重激发态及其电子转移反应性的因素。 各种分子的稳定阴离子和阳离子自由基将通过化学还原或氧化制备，然后通过皮秒瞬态吸收和荧光光谱法表征其物理性质。 待确定的关键参数包括双重激发态的寿命和能量，沿着辐射和非辐射衰变速率常数。 实验结果将被用来通知离子自由基双重激发态的结构-性质关系，具体的目的是描绘它们的能量和非辐射衰变率之间是否存在能隙定律的相关性。 理论将被用来识别分子系统，优化方面的双重激发态能量和寿命，从而指导优化的电子转移光敏剂的设计。这个奖项反映了NSF的法定使命，并已被认为是值得通过评估使用基金会的智力价值和更广泛的影响审查标准的支持。