CAREER: SusChEM: Computational Studies of Light-Induced Dynamics in First-Row Transition Metal Complexes

职业：SusChEM：第一行过渡金属配合物光致动力学的计算研究

• 批准号: 1554855
• 负责人: Elena Jakubikova
• 金额: $ 57.5万
• 依托单位: North Carolina State University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2016
• 资助国家: 美国
• 起止时间: 2016-04-01 至 2023-03-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1554855&HistoricalAwards=false
• 关键词: CAREER; SusChEM; Computational; Studies; Light

In this CAREER project funded by the Chemical Structure, Dynamics & Mechanism B Program of the Chemistry Division, Professor Elena Jakubikova of the Department of Chemistry at North Carolina State University investigates how transition metal complexes based on earth-abundant metals interact with light. The goal of this project is to utilize computer modeling to obtain a deeper understanding of structure-property relationships in such complexes, so that new chromophores, photocatalysts or photomagnetic materials may be designed. The project lies at the interface of computational, inorganic, and physical chemistry, and is therefore well positioned to introduce computational chemistry as a valuable tool to a wide range of students at the high school, undergraduate and graduate levels. Collection of dyes in the Max A. Weaver Dye Library at North Carolina State University is used to motivate the research and educational activities of high school and undergraduate students. The students contribute developing a set of data for the library to benchmark computational methodologies for calculations of visible absorption spectra and to screen dyes for use as chromophores in dye-sensitized solar cells.The rational design of chromophores and photocatalysts based on first row transition metal complexes relies on the fundamental knowledge of how these complexes absorb and dissipate light. In particular, understanding the mechanisms of nonradiative decay processes, such as internal conversion and intersystem crossing, is key to our ability to control excited state properties of these systems. The goal of this project is to obtain a better theoretical understanding of the mechanism of nonradiative decay in first row transition metal complexes, so that a more rational approach to the development of efficient chromophores, photocatalysts, and photomagnetic materials based on earth-abundant metals can be taken. Specifically, the project focuses on structural factors that facilitate the ultrafast intersystem crossing events in iron-based complexes. The project involves computational studies on a series of octahedral as well as low coordinate iron complexes utilizing density functional theory, time-dependent density functional theory, nonadiabatic transition state theory, and nonadiabatic surface hopping dynamics. Minority and economically disadvantaged students are recruited through the existingrelationships with the NC Project SEED program and the NSF-Research Experiences for Undergraduates Program in the Department of Chemistry. Local high school teachers are provided with the tools and expertiseto develop and implement their own computational chemistry modules into the Advanced Placement Chemistry curriculum using the North Carolina High School Computational Chemistry Server.

在这个由化学系化学结构、动力学和机理 B 项目资助的职业项目中，北卡罗来纳州立大学化学系的 Elena Jakubikova 教授研究了基于地球丰富金属的过渡金属配合物如何与光相互作用。该项目的目标是利用计算机建模来更深入地了解此类复合物的结构-性能关系，以便设计新的发色团、光催化剂或光磁材料。该项目位于计算化学、无机化学和物理化学的交汇处，因此能够很好地向高中、本科和研究生水平的广大学生介绍计算化学作为一种有价值的工具。北卡罗来纳州立大学 Max A. Weaver 染料图书馆收集的染料用于激发高中生和本科生的研究和教育活动。 学生们为图书馆开发了一组数据，以对计算可见吸收光谱的计算方法进行基准测试，并筛选用作染料敏化太阳能电池中发色团的染料。基于第一行过渡金属配合物的发色团和光催化剂的合理设计依赖于这些复合物如何吸收和消散光的基础知识。特别是，了解非辐射衰变过程的机制，例如内部转换和系间交叉，是我们控制这些系统的激发态特性的能力的关键。该项目的目标是更好地理论理解第一排过渡金属配合物的非辐射衰变机制，以便更合理地开发基于地球丰富金属的高效生色团、光催化剂和光磁材料。被采取。具体来说，该项目重点关注促进铁基复合体中超快系间穿越事件的结构因素。该项目涉及利用密度泛函理论、瞬态密度泛函理论、非绝热过渡态理论和非绝热表面跳跃动力学对一系列八面体和低配位铁配合物进行计算研究。 少数民族和经济困难学生是通过与 NC 项目 SEED 计划和化学系 NSF 本科生研究经验计划的现有关系招募的。 为当地高中教师提供工具和专业知识，以使用北卡罗来纳州高中计算化学服务器开发自己的计算化学模块并将其纳入大学先修化学课程中。

项目成果

Isocyanide Ligands Promote Ligand-to-Metal Charge Transfer Excited States in a Rhenium(II) Complex

异氰化物配体促进铼(II)配合物中配体到金属的电荷转移激发态

• DOI: 10.1021/acs.inorgchem.2c03193
• 发表时间: 2023-05
• 期刊: Inorganic Chemistry
• 影响因子: 4.6
• 作者: Rodriguez, Tayliz M.;Deegbey, Mawuli;Chen, Chun;Jakubikova, Elena;Dempsey, Jillian L.
• 通讯作者: Dempsey, Jillian L.

Approximating Periodic Potential Energy Surfaces with Sparse Trigonometric Interpolation

用稀疏三角插值逼近周期势能面

• DOI: 10.1021/acs.jpcb.9b08210
• 发表时间: 2019-11
• 期刊: The Journal of Physical Chemistry B
• 作者: Morrow, Zack;Liu, Chang;Kelley, C. T.;Jakubikova, Elena
• 通讯作者: Jakubikova, Elena

Tuning the Redox Potentials and Ligand Field Strength of Fe(II) Polypyridines: The Dual π-Donor and π-Acceptor Character of Bipyridine

调节 Fe(II) 聚吡啶的氧化还原电位和配体场强度：联吡啶的双重 β 供体和 β 受体特征

• DOI: 10.1021/acs.inorgchem.8b01002
• 发表时间: 2018-04
• 期刊: Inorganic Chemistry
• 影响因子: 4.6
• 作者: Ashley, Daniel C.;Jakubikova, Elena
• 通讯作者: Jakubikova, Elena

Predicting the electrochemical behavior of Fe(II) complexes from ligand orbital energies

从配体轨道能量预测 Fe(II) 配合物的电化学行为

• DOI: 10.1016/j.jphotochem.2019.01.026
• 发表时间: 2019-05-01
• 期刊: Journal of Photochemistry and Photobiology A: Chemistry
• 作者: D. Ashley;E. Jakubikova
• 通讯作者: E. Jakubikova

Ironing out the photochemical and spin-crossover behavior of Fe(II) coordination compounds with computational chemistry

用计算化学解决 Fe(II) 配位化合物的光化学和自旋交叉行为

• DOI: 10.1016/j.ccr.2017.02.005
• 发表时间: 2017-04-15
• 期刊: Coordination Chemistry Reviews
• 影响因子: 20.6
• 作者: D. Ashley;E. Jakubikova
• 通讯作者: E. Jakubikova