CAREER: Resonant Hartree-Fock Inspired Descriptions of Excited State Processes

职业生涯：共振 Hartree-Fock 启发的激发态过程描述

• 批准号: 2144905
• 负责人: Lee Thompson
• 金额: $ 65万
• 依托单位: University of Louisville Research Foundation Inc
• 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: 2022-04-01 至 2027-03-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2144905&HistoricalAwards=false
• 关键词: CAREER; Resonant; Hartree; Fock; Inspired

With support from the Chemical Theory, Models and Computational Methods (CTMC) Program in the Division of Chemistry and the Established Program to Stimulate Competitive Research (EPSCoR), Lee M. Thompson of University of Louisville is developing computational approaches to simulate excited state processes of relevance to metallo-photocatalysis. Metallo-photocatalysis combines transition metal catalysis and photoredox catalysis to enable new molecular synthesis approaches. However, several competing mechanisms for catalyst activation can potentially lead to different reaction products, and so computational modelling is beneficial to establish the rates of excited state processes and design catalytic systems that enhance the desired reactivity. For this, modeling challenges exist, including: (i) the size of the systems involved, (ii) the nature of the electronic structure of these systems as these are often not amenable to current approximations embodied in reduced-CPU (central processing unit) time methods, and (iii) theoretical formalisms requiring computation of terms that are difficult to extract from simulation. To resolve these difficulties, Dr. Thompson is developing computational methods that couple together low-cost approximations that each capture different features of the electronic structure. The aim is to develop a general computational platform of more accurate approaches that takes advantage of partitioning of the electronic interactions to reduce computational efforts. This project also includes the development of an integrated education plan focusing on programming literacy and sustainable software development that aims to provide students with a deeper understanding of physical chemistry and computational science. The principal investigator is also working to build a forum to engage stakeholders in the chemistry enterprise in Louisville, KY through the Derby lecture series. This project on Resonant Hartree-Fock inspired descriptions of excited state processes consists of two main scientific goals. First, the Thompson research team is developing algorithms that explore self-consistent field (SCF) solution space to understand how the SCF function landscape encodes different correlation mechanisms. The methods permit enumeration of SCF solutions from which a short determinant expansion can be chosen that spans relevant correlation mechanisms present in molecular systems. Additionally, the SCF solutions can be used as references for post-SCF methods. Second, models that optimize a different-orbitals-for-different-configurations wavefunction to account for interactions between the different correlation mechanisms are being designed and implemented. The resulting wavefunction is being used as a platform to recover remaining correlation energy at reduced computational cost. The new methods will be applied to the study of photo-induced electron transfer and excitation energy transfer rates in metallo-photocatalytic systems. These tools, if successful, could have a significant impact on the design of new photoredox catalyst systems and processes, an area of great current interest in reaction development.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.

在化学理论，模型和计算方法（CTMC）方案的支持下，刺激竞争研究的既定计划（EPSCOR），路易斯维尔大学的Lee M. Thompson正在开发计算方法，以模拟激发的状态过程与金属催化性的相关性。金属 - 光催化结合了过渡金属催化和光电氧催化，以实现新的分子合成方法。但是，催化剂激活的几种竞争机制可能会导致不同的反应产物，因此计算建模有益于建立激发态过程和设计催化系统的速率，从而增强所需的反应性。为此，存在建模挑战，包括：（i）所涉及的系统的大小，（ii）这些系统的电子结构的性质，因为这些系统通常不适合在还原CPU（中央处理单元）体现的当前近似值。时间方法和（iii）的理论形式主义需要计算难以从模拟中提取的术语。为了解决这些困难，汤普森博士正在开发计算方法，这些方法将低成本近似值融合在一起，每个近似值捕获了电子结构的不同特征。目的是开发一个更准确的方法的一般计算平台，该平台利用电子相互作用来减少计算工作。该项目还包括制定综合教育计划，该计划着重于编程素养和可持续软件开发，旨在为学生提供对物理化学和计算科学的更深入的了解。 首席研究人员还致力于建立一个论坛，通过德比讲座系列与肯塔基州路易斯维尔的化学企业参与利益相关者。这个关于共鸣的Hartree-fock启发的项目的项目启发了激发状态过程的描述，包括两个主要的科学目标。首先，汤普森研究团队正在开发探索自洽场（SCF）解决方案空间的算法，以了解SCF功能景观如何编码不同的相关机制。该方法允许列举SCF溶液，从中可以选择跨越分子系统中存在相关相关机制的简短决定因素扩展。此外，SCF解决方案可用作SCF后方法的参考。其次，正在设计和实现优化不同相关机制之间相互作用的不同轨道的模型，以解释不同的相互作用。最终的波函数被用作平台，以降低的计算成本恢复剩余的相关能量。新方法将应用于金属催化系统中光诱导的电子传递和激发能量传递速率。 这些工具，如果成功的话，可能会对新的Photoredox催化剂系统和流程的设计产生重大影响，这是当前对反应开发的极大兴趣的领域。该奖项反映了NSF的法定任务，并被认为是通过基金会的评估来获得的支持。智力优点和更广泛的影响审查标准。

项目成果

Nonorthogonal Active Space Decomposition of Wave Functions with Multiple Correlation Mechanisms

• DOI: 10.1021/acs.jpclett.2c03349
• 发表时间: 2022-12-21
• 期刊: JOURNAL OF PHYSICAL CHEMISTRY LETTERS
• 影响因子: 5.7
• 作者: Kempfer-Robertson, Emily M.;Mahler, Andrew D.;Thompson, Lee M.
• 通讯作者: Thompson, Lee M.

Role of Exact Exchange in Difference Projected Double-Hybrid Density Functional Theory for Treatment of Local, Charge Transfer, and Rydberg Excitations

精确交换在处理局部、电荷转移和里德伯激励的差分投影双混合密度泛函理论中的作用

• DOI: 10.1021/acs.jpca.2c04338
• 发表时间: 2022
• 期刊: The Journal of Physical Chemistry A
• 作者: Kempfer-Robertson, Emily M.;Haase, Meagan N.;Bersson, Jonathan S.;Avdic, Irma;Thompson, Lee M.
• 通讯作者: Thompson, Lee M.