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 获得化学系化学理论、模型和计算方法项目的奖项支持，致力于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（例如光合作用和呼吸作用）中起着至关重要的作用。 它们还在技术中发挥着作用，例如在太阳能电池的能源生产中。 开发计算方法来准确描述这种耦合具有挑战性。 电子和质子太轻，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。这些方法适用于生物和化学相关的特定过程。 Hammes-Schiffer 研究小组还维护和增强了一个包含与该主题相关的软件和教育工具的网站。 该网站上提供的计算机程序、工具、演示和教程将使各个领域的科学家能够了解该主题。 此外，该项目通过更好地理解电子和质子之间的耦合，促进技术和生物医学的进步。 一个重要的例子是更有效的太阳能电池和其他替代性可再生能源的设计。 另一个例子是通过修饰依赖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，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领域发挥着至关重要的作用流程。要研究的具体问题包括核量子效应的作用，例如质子离域和零点能量，以及非玻恩-奥本海默效应，这些效应在这些类型的反应中通常很重要。 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，该方法在与框架内的电子相同的量子力学水平上处理关键原子核，例如转移的质子的 DFT。 重点是开发多分量时间相关 DFT (NEO-TDDFT) 方法，用于计算激发电子、质子振动和电子-质子振动态。 该方法用于计算光诱导质子转移和 PCET 系统的激发能量和跃迁密度。 NEO-DFT 和 NEO-TDDFT 方法正在被纳入公开可用的电子结构包中。 此外，我们正在创建教程来解释如何执行 NEO 计算并强调这种方法的独特功能。 此外，PCET 网站正在得到增强，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，并通过使用基金会的评估进行评估，认为值得支持。智力价值和更广泛的影响审查标准。

项目成果

Controlling Electrons and Protons through Theory: Molecular Electrocatalysts to Nanoparticles

通过理论控制电子和质子：纳米粒子的分子电催化剂

• DOI: 10.1021/acs.accounts.8b00240
• 发表时间: 2018-08
• 期刊: Accounts of Chemical Research
• 影响因子: 18.3
• 作者: Hammes

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: 2019-09
• 期刊: The Journal of Chemical Physics
• 作者: Tao, Zhen;Yang, Yang;Hammes
• 通讯作者: Hammes

Multicomponent Quantum Chemistry: Integrating Electronic and Nuclear Quantum Effects via the Nuclear–Electronic Orbital Method

多组分量子化学：通过核电子轨道方法整合电子和核量子效应

• DOI: 10.1021/acs.chemrev.9b00798
• 发表时间: 2020-05
• 期刊: Chemical Reviews
• 影响因子: 62.1
• 作者: Pavošević, Fabijan;Culpitt, Tanner;Hammes
• 通讯作者: Hammes

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: 2020-05
• 期刊: The Journal of Physical Chemistry Letters
• 作者: Zhao, Luning;Tao, Zhen;Pavošević, Fabijan;Wildman, Andrew;Hammes;Li, Xiaosong
• 通讯作者: Li, Xiaosong

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: 2018-03
• 期刊: The Journal of Physical Chemistry Letters
• 作者: Yang, Yang;Culpitt, Tanner;Hammes
• 通讯作者: Hammes