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

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教授研究了基于富含地球的金属的过渡金属络合物如何与光相互作用。这个项目的目标是利用计算机模拟来更深入地了解这类络合物中的结构-性质关系，以便设计新的生色团、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界处，因此能够很好地将计算化学作为一种有价值的工具介绍给高中、本科和研究生水平的广泛学生。北卡罗来纳州立大学马克斯·A·韦弗染料图书馆的染料收藏被用来激励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，以基准计算可见吸收光谱的计算方法，并筛选染料用作染料敏化太阳能电池的生色团。基于第一排过渡金属络合物的生色团和光催化剂的合理设计依赖于这些络合物如何吸收和消散光的基本知识。特别是，了解非辐射衰变过程的机制，如内部转换和系统间交叉，是我们控制这些系统激发态性质的关键。本项目的目标是从理论上更好地理解第一排过渡金属络合物的非辐射衰变机理，从而为开发基于地球上丰富的金属的高效生色团、光催化剂和光磁材料提供更合理的途径。具体地说，该项目侧重于促进铁基复合体中超快系统间交叉事件的结构因素。该项目利用密度泛函理论、含时密度泛函理论、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络合物进行了计算研究。少数民族和经济困难学生是通过与NC项目种子计划和NSF-化学系本科生研究经验计划的现有关系来招收的。使用北卡罗来纳州高中计算化学服务器，为当地高中教师提供了开发和实施他们自己的计算化学模块到高级选修化学课程中的工具和专业知识。

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.