Non-Born-Oppenheimer Effects in the Framework of Multicomponent Time-Dependent Density Functional Theory

多分量时变密度泛函理论框架中的非玻恩奥本海默效应

• 批准号: 1762018
• 负责人: Sharon Hammes-Schiffer
• 金额: $ 32万
• 依托单位: Yale University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2018
• 资助国家: 美国
• 起止时间: 2018-08-01 至 2020-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1762018&HistoricalAwards=false
• 关键词: Non; Born; Oppenheimer; Effects; Framework

Sharon Hammes-Schiffer of Yale University is supported by an award from the Chemical Theory, Models and Computational Methods program in the Division of Chemistry to develop computational approaches to study the interaction between electrons and protons in chemical systems. The coupling between electrons and protons plays a vital role in many important biological processes such as photosynthesis and respiration. They also play a role in technology, for example, in energy production in solar cells. Developing computational methods to accurately describe this coupling is challenging. Electrons and protons are so light that they must be treated quantum mechanically. Hammes-Schiffer and her coworkers develop quantum mechanics methods that are computationally efficient. These methods are applied to specific processes of biological and chemical relevance. The Hammes-Schiffer research group also maintains and enhances a website containing software and educational tools related to this topic. The computer programs, tools, demonstrations, and tutorials available on this web site will enable scientists in a broad range of fields to learn about this topic. In addition, this project facilitates technological and biomedical advances through a better understanding of the coupling between electrons and protons. An important example is the design of more effective solar cells and other alternative, renewable energy sources. Another example is the design of more effective drugs through modification of enzymes that rely on the coupling between electrons and protons. The objective of this project is to develop new theoretical and computational approaches that will provide insight into the underlying fundamental principles of photoinduced proton transfer and proton-coupled electron transfer (PCET) reactions, which play a vital role in a broad range of biological and chemical processes. The specific issues to be examined include the roles of nuclear quantum effects, such as proton delocalization and zero-point energy, as well as non-Born-Oppenheimer effects, which are often significant in these types of reactions. The method development is conducted within the framework of the nuclear-electronic orbital density functional theory (NEO-DFT) approach, which treats key nuclei, such as the transferring proton(s), quantum mechanically on the same level as the electrons within the framework of DFT. The focus is to develop the multicomponent time-dependent DFT (NEO-TDDFT) approach for calculating excited electronic, proton vibrational, and electron-proton vibronic states. This approach is used to compute excitation energies and transition densities for photoinduced proton transfer and PCET systems. The NEO-DFT and NEO-TDDFT approaches is being incorporated into a publicly available electronic structure package. In addition, tutorials are being created to explain how to perform NEO calculations and to highlight the unique capabilities of this approach. Furthermore, a web site on PCET is being enhanced to convey useful information to the community and to provide useful tools, scripts, and programs relevant to studying PCET.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.

耶鲁大学的Sharon Hammes-Schiffer获得了化学系化学理论，模型和计算方法项目的奖项，以开发计算方法来研究化学系统中电子和质子之间的相互作用。电子和质子之间的耦合在许多重要的生物过程中起着至关重要的作用，如光合作用和呼吸作用。 它们还在技术方面发挥作用，例如在太阳能电池的能源生产方面。 开发计算方法来准确描述这种耦合是具有挑战性的。 电子和质子非常轻，必须用量子力学来处理。 Hammes-Schiffer和她的同事开发了计算效率高的量子力学方法。这些 方法被应用于生物和化学相关的特定过程。 Hammes-Schiffer研究小组还维护和加强了一个网站，其中载有与这一主题有关的软件和教育工具。 本网站提供的计算机程序、工具、演示和教程将使各个领域的科学家能够了解这一主题。 此外，该项目通过更好地理解电子和质子之间的耦合促进了技术和生物医学的进步。 一个重要的例子是设计更有效的太阳能电池和其他替代性可再生能源。 另一个例子是通过修饰依赖于电子和质子之间耦合的酶来设计更有效的药物。该项目的目标是开发新的理论和计算方法，以深入了解光诱导质子转移和质子耦合电子转移（PCET）反应的基本原理，这些反应在广泛的生物和化学过程中发挥着至关重要的作用。要研究的具体问题包括核量子效应的作用，如质子离域和零点能，以及非玻恩-奥本海默效应，这在这些类型的反应中往往是显着的。 该方法的开发是在核电子轨道密度泛函理论（NEO-DFT）方法的框架内进行的，该方法将关键核（例如转移质子）以与DFT框架内的电子相同的水平进行量子力学处理。 重点是开发多组分含时DFT（NEO-TDDFT）方法计算激发电子，质子振动，电子-质子振动态。 这种方法被用来计算光诱导质子转移和PCET系统的激发能和跃迁密度。 近地天体-密度泛函理论和近地天体-TDDFT方法正在被纳入一套公开提供的电子结构。 此外，正在编写教程，解释如何进行近地天体计算，并强调这一方法的独特能力。 此外，一个关于PCET的网站正在得到加强，以向社区传达有用的信息，并提供与研究PCET相关的有用工具、脚本和程序。该奖项反映了NSF的法定使命，并被认为值得通过使用基金会的知识价值和更广泛的影响审查标准进行评估来支持。

项目成果

Real-Time Time-Dependent Nuclear−Electronic Orbital Approach: Dynamics beyond the Born–Oppenheimer Approximation

实时瞬态核电子轨道方法：超越玻恩奥本海默近似的动力学

• DOI: 10.1021/acs.jpclett.0c00701
• 发表时间: 2020
• 期刊: The Journal of Physical Chemistry Letters
• 作者: Zhao, Luning;Tao, Zhen;Pavošević, Fabijan;Wildman, Andrew;Hammes-Schiffer, Sharon;Li, Xiaosong
• 通讯作者: Li, Xiaosong

Multicomponent density functional theory: Including the density gradient in the electron-proton correlation functional for hydrogen and deuterium

多组分密度泛函理论：包括氢和氘的电子-质子相关泛函中的密度梯度

• DOI: 10.1063/1.5119124
• 发表时间: 2019
• 期刊: The Journal of Chemical Physics
• 作者: Tao, Zhen;Yang, Yang;Hammes-Schiffer, Sharon
• 通讯作者: Hammes-Schiffer, Sharon

Stability conditions and local minima in multicomponent Hartree-Fock and density functional theory

多组分 Hartree-Fock 和密度泛函理论中的稳定性条件和局部最小值

• DOI: 10.1063/1.5040353
• 发表时间: 2018
• 期刊: The Journal of Chemical Physics
• 作者: Yang, Yang;Culpitt, Tanner;Tao, Zhen;Hammes-Schiffer, Sharon
• 通讯作者: Hammes-Schiffer, Sharon

Multicomponent Time-Dependent Density Functional Theory: Proton and Electron Excitation Energies

多组分时变密度泛函理论：质子和电子激发能

• DOI: 10.1021/acs.jpclett.8b00547
• 发表时间: 2018
• 期刊: The Journal of Physical Chemistry Letters
• 作者: Yang, Yang;Culpitt, Tanner;Hammes-Schiffer, Sharon
• 通讯作者: Hammes-Schiffer, Sharon

Molecular Vibrational Frequencies with Multiple Quantum Protons within the Nuclear-Electronic Orbital Framework

核电子轨道框架内多个量子质子的分子振动频率

• DOI: 10.1021/acs.jctc.9b00665
• 发表时间: 2019
• 期刊: Journal of Chemical Theory and Computation
• 影响因子: 5.5
• 作者: Culpitt, Tanner;Yang, Yang;Schneider, Patrick E.;Pavošević, Fabijan;Hammes-Schiffer, Sharon
• 通讯作者: Hammes-Schiffer, Sharon