Multiconfiguration Pair-Density Functional Theory for Spectroscopy and Photochemistry

光谱学和光化学的多配置对密度泛函理论

• 批准号: 2054723
• 负责人: Laura Gagliardi
• 金额: $ 55万
• 依托单位: University of Chicago
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2021
• 资助国家: 美国
• 起止时间: 2021-08-01 至 2024-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2054723&HistoricalAwards=false
• 关键词: Multiconfiguration; Pair; Density; Functional; Theory

With support from the Chemical Theory, Models and Computational Methods Program in the Chemistry Division, Professors Laura Gagliardi of the University of Chicago and Donald G. Truhlar of the University of Minnesota will develop multi-configuration pair-density functional theory (MC-PDFT) and employ it to compute potential energy surfaces for ground and excited states. As collaborators, the two principal investigators are developing computational methods that will likely advance knowledge across a broad range of chemical space, from catalysis, to photochemistry, supramolecular chemistry, spectroscopy, thermochemistry, materials chemistry, biochemistry, and atmospheric chemistry. The new computational tools are expected to help elucidate phenomena identified by experimentalists and predict new chemical behavior in these areas. The work proposed here aims to demonstratively high levels of accuracy and applicability for quantum chemical methods. Moreover, the team will continue to develop codes that will be available in open-source packages to the community, including considerable effort into documentation. Additionally, the combined expertise of two senior investigators will allow students and postdocs to benefit from a wide range of ideas that will contribute to a well-rounded career preparation.Laura Gagliardi and Donald G. Truhlar are developing pair-density functional theory (MC-PDFT) with new types of wave functions, including localized active space wave functions, in order to exploit the localized character of some important kinds of strong electron correlation. This method will be advanced and employed to explore transition metal complexes involved in catalysis and excited states involved in photochemical reactions. Such systems often have a complex electronic structure that cannot be well described even to zero order by only a single electronic configuration, that is, by a single way of distributing the electrons in orbitals. MC-PDFT can be viewed as a way to combine wave function theory (WFT) and density functional theory (DFT) to take advantage of their respective strengths. In particular, the team proposes to develop MC-PDFT with the following objectives: i) Develop pair-density functional theory with new types of wave functions, including localized active space wave functions, in order to exploit the localized character of some important kinds of strong electron correlation, so as to enable the construction of accurate electronic structure calculations for extended chemical systems such as metal-organic frameworks, metal-ligand complexes, and molecules containing multiple weakly-coupled -orbital subsystems. ii) Derive and implement analytic Hessians for MC-PDFT so that one can determine whether a stationary point is a local minimum or saddle point and then calculate vibrational frequencies at this level of theory. This will allow the team and the community to use MC-PDFT as a next-generation tool to compute potential energy surfaces for ground and excited states. iii) Explore new kinds of density functionals based on the unpaired density and the first-order reduced density matrix, to improve the accuracy of the theory. iv) Apply the methods above to transition metal systems, spectroscopy, and photochemistry.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，模型和计算方法计划的支持下，芝加哥大学的Laura Gagliardi教授和明尼苏达大学的Donald G. Truhlar将开发多配置对配对密度功能理论（MC-PDFT），并采用它来计算地面和激发状态的势能表面。作为合作者，两位主要研究人员正在开发计算方法，这些方法可能会跨越广泛的化学空间知识，从催化，光化学到光化学，超分子化学，光谱，热化学，材料化学，生物化学和大气化学。 期望新的计算工具有助于阐明实验者确定的现象，并预测这些领域的新化学行为。这里提出的工作旨在表现出高度的量子化学方法的准确性和适用性。此外，该团队将继续开发代码，这些代码将以开源软件包为社区提供，包括在文档中进行大量精力。此外，两名高级研究人员的综合专业知识将允许学生和博士后从广泛的想法中受益，这些想法将有助于全面的职业准备。该方法将被提前并用于探索与光化学反应有关的参与催化和激发态的过渡金属复合物。这样的系统通常具有复杂的电子结构，即使仅通过单个电子构型也可以通过单一的方式将电子分配在轨道中。 MC-PDFT可以看作是结合波函数理论（WFT）和密度功能理论（DFT）的一种方式，以利用其各自的优势。特别是，该团队建议通过以下目标开发MC-PDFT：i）开发具有新型波功能的配对密度功能理论，包括局部活动空间波函数，以利用某些重要类型的强电子相关性的本地性特征，以便启用诸如金属构造的扩展化学系统的精确电子结构，以构建精确的电子结构。弱耦合 - 轨道子系统。 ii）为MC-PDFT得出并实施分析性HESSIAN，以便可以确定固定点是局部最小值还是鞍点，然后在此理论水平上计算振动频率。这将使团队和社区可以使用MC-PDFT作为下一代工具，以计算地面和激发状态的势能表面。 iii）根据未配对的密度和一阶降低密度矩阵探索新型的密度功能，以提高理论的准确性。 iv）将上述方法应用于过渡金属系统，光谱和光化学。该奖项反映了NSF的法定任务，并被认为是值得通过基金会的知识分子优点和更广泛的影响评估标准通过评估来支持的。

项目成果

Application of Multiconfiguration Pair-Density Functional Theory to the Diels–Alder Reaction

多构型对密度泛函理论在Diels-Alder反应中的应用

• DOI: 10.1021/acs.jpca.2c06433
• 发表时间: 2022
• 期刊: The Journal of Physical Chemistry A
• 作者: Mitchell, Erica C.;Scott, Thais R.;Bao, Jie J.;Truhlar, Donald G.
• 通讯作者: Truhlar, Donald G.

Performance of Screened-Exchange Functionals for Band Gaps and Lattice Constants of Crystals

晶体带隙和晶格常数的屏蔽交换泛函的性能

• DOI: 10.1021/acs.jctc.2c00822
• 发表时间: 2023
• 期刊: Journal of Chemical Theory and Computation
• 影响因子: 5.5
• 作者: Cheng Zhang;Pragya Verma;Jiaxu Wang;Yiwei Liu;Xiao He;Ying Wang;Donald G. Truhlar;Zhonghua Liu
• 通讯作者: Zhonghua Liu

Decomposition of the Electronic Energy in Terms of Density, Density Coherence, and the Connected Part of the Two-Body Reduced Density Matrix

电子能量的密度分解、密度相干性和二体约化密度矩阵的连通部分

• DOI: 10.1021/acs.jctc.1c00679
• 发表时间: 2021
• 期刊: Journal of Chemical Theory and Computation
• 影响因子: 5.5
• 作者: Zhang, Dayou;Truhlar, Donald G.
• 通讯作者: Truhlar, Donald G.

Analytic gradients for compressed multistate pair-density functional theory

压缩多态对密度泛函理论的解析梯度

• DOI: 10.1080/00268976.2022.2110534
• 发表时间: 2022
• 期刊: Molecular Physics
• 影响因子: 1.7
• 作者: Bao, Jie J.;Hermes, Matthew R.;Scott, Thais R.;Sand, Andrew M.;Lindh, Roland;Gagliardi, Laura;Truhlar, Donald G.
• 通讯作者: Truhlar, Donald G.

Nonadiabatic Molecular Dynamics by Multiconfiguration Pair-Density Functional Theory

• DOI: 10.1021/acs.jctc.1c01048
• 发表时间: 2022-01-14
• 期刊: JOURNAL OF CHEMICAL THEORY AND COMPUTATION
• 影响因子: 5.5
• 作者: Calio, Paul B.;Truhlar, Donald G.;Gagliardi, Laura
• 通讯作者: Gagliardi, Laura