CAREER: Coupled electronic and nuclear dynamics in organometallic enzymes and photocatalysts

加州理工学院的托马斯·米勒得到了化学部理论、模型和计算方法计划的支持，他开发了新的理论方法来了解有机金属催化剂和光催化酶中耦合的电子和核动力学。这些方法旨在克服模拟和理解过程动力学的内在挑战，这些过程是太阳光催化的核心，包括蛋白质中的远程电子转移动力学，氧化还原耦合的质子转移动力学，以及酶中的多电子转移事件。这项工作有两个目标：1)通过发展一种通用的嵌入密度泛函理论(e-DFT)方法，将大系统中的多电子问题归结为少电子问题，以获得对大系统电子结构的简化描述。2)通过将环-聚合物分子动力学(RPMD)方法和e-DFT方法相结合来模拟光催化剂和酶中的反应动力学，获得了对质子耦合电子转移(PCET)动力学的新见解。合理设计分子光系统是一个具有极其重要的科学、工业和社会意义的挑战。计算研究有可能在这一领域做出非凡的贡献，因为它允许对生物光系统进行详细的研究，通过揭示对基本光化学过程的关键见解，通过允许快速和廉价地筛选合成光催化剂。米勒教授和他的研究小组还参与了一项新的推广工作，即三叉戟计划-团队研究产生综合教育工具。三叉戟是一个分三个阶段的项目，其中(I)一个由PI、当地一名高中生和当地科学教师组成的团队在一个计算暑期研究项目上进行合作，(Ii)团队利用研究中形成的技能和想法，制定一项计划，将计算研究软件整合到S老师的课堂中，以及(Iii)PI访问课堂，以获得对计划实施的反馈，以完善计划，并讨论科学职业。三叉戟为当地公立学校的教师和学生提供可持续的教育支持。

Thomas Miller of the California Institute of Technology is supported by an award from the Theory, Models and Computational Methods program in the Chemistry division to develop new theoretical methods to understand coupled electronic and nuclear dynamics in organometallic catalysts and photocatalytic enzymes. These methods are designed to overcome the intrinsic challenges of simulating and understanding the dynamics of processes that are central to solar photocatalysis, including long range electron transfer dynamics in proteins, redox-coupled proton transfer dynamics, and multiple electron transfer events in enzymes. The work has two objectives:1) Reducing many-electron problems to few-electron problems in large-scale systems by developing a general embedded density functional theory (e-DFT) approach to obtain reduced descriptions for the electronic structure of large-scale systems. 2) Obtaining new insights into proton-coupled electron transfer (PCET) dynamics by combinging the ring-polymer molecular dynamics (RPMD) method with the e-DFT approach to simulate reaction dynamics in photcatalysts and enzymes.The rational design of molecular photosystems is a challenge of paramount scientific, industrial, and societal importance. Computational research has the potential to make extraordinary contributions in this area by allowing for detailed investigations of biological photosystems, by revealing key insights into fundamental photochemical processes, and by allowing for fast and inexpensive screening of synthetic photocatalysts. Prof. Miller and his research group are also engaged in a novel outreach effort, the TRIDENT Program - Team Research yielding Integrated Educational Tools. TRIDENT is a three-stage program in which (i) a team composed of the PI, a local high-school student, and local science teacher collaborates on a computational summer research project, (ii) using skills and ideas developed through the research, the team tailors a plan to integrate computational research software into the teacher?s classroom, and (iii) the PI visits the classroom to gain feedback on the implementation of the plan, to refine the plan, and to discuss careers in science. TRIDENT provides sustainable educational support to teachers and students at local public schools.