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

耶鲁大学的Sharon Hammes-Schiffer教授获得了化学系化学理论，模型和计算方法项目的奖励，以开发描述电子和质子在化学过程中作用的计算方法。电子和质子的相互作用或耦合在广泛的生物和化学过程中起着至关重要的作用，包括光合作用，呼吸作用和太阳能电池中的能量产生。精确描述这种耦合的计算方法的发展是具有挑战性的，因为电子和质子非常轻，必须对它们进行特殊处理，这在计算上是昂贵的。Hammes-Schiffer教授正在开发以计算实用的方式描述电子和质子的方法。她正在将这些方法应用于生物和化学相关的特定过程，以阐明这些过程的基本原理。此外，她和她的研究小组正在将这些计算方法纳入已建立的量子化学软件包中，以使一般科学界受益。Hammes-Schiffer教授还维护和加强了一个网站，其中包含软件和教育工具，包括计算机程序，工具，演示和教程。这项研究促进了更有效的太阳能电池和其他可再生能源的技术和生物医学进步，并提高了对酶的理解。Hammes-Schiffer教授正在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。这些方法的目的是包括核量子效应，如质子离域和零点能，以及非玻恩-奥本海默效应，在计算上的实际方式。Hammes-Schiffer正在核电子轨道密度泛函理论（NEO-DFT）方法的框架内开发这些方法，该方法在DFT框架内将关键核（如转移质子）与电子在同一水平上进行量子力学处理。多组分含时密度泛函（NEO-TDDFT）方法可以计算激发电子、质子振动和电子-质子振动态。Hammes-Schiffer正在开发近地天体方法，用于计算质子转移和PCET反应的最小能量路径和隧道分裂，以及光致反应的混合电子-质子振动激发态。她还在开发实时近地天体-TDDFT方法和其他非绝热动力学方法，用于模拟超快电子和核动力学，目标是应用于光致PCET反应。她正在将这些方法纳入成熟的量子化学软件包，并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，她正在维护和加强一个关于PCET的网站，以向社区传达有用的信息，并提供与研究PCET相关的有价值的工具、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。

Professor 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 methods for describing the role of electrons and protons in chemical processes. The interaction or coupling of electrons and protons plays a vital role in a wide range of biological and chemical processes, including photosynthesis, respiration, and energy production in solar cells. The development of computational methods that accurately describe this coupling is challenging because electrons and protons are so light that they must be treated specially, which is computationally expensive. Professor Hammes-Schiffer is developing methods that describe electrons and protons in a computationally practical manner. She is applying these methods to specific processes of biological and chemical relevance to elucidate the fundamental principles of these processes. In addition, she and her research group are incorporating these computational methods into established quantum chemistry software packages to benefit the general scientific community. Professor Hammes-Schiffer is also maintaining and enhancing a website containing software and educational tools including computer programs, tools, demonstrations, and tutorials. This research facilitates technological and biomedical advances in more effective solar cells and other renewable energy sources as well as improved understanding of enzymes. Professor Hammes-Schiffer is developing new theoretical and computational approaches that 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. These approaches are designed to include nuclear quantum effects, such as proton delocalization and zero-point energy, as well as non-Born-Oppenheimer effects, in a computationally practical manner. Hammes-Schiffer is developing these methods 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 multicomponent time-dependent DFT (NEO-TDDFT) approach enables the calculation of excited electronic, proton vibrational, and electron-proton vibronic states. Hammes-Schiffer is developing NEO methods for computing minimum energy paths and tunneling splittings for proton transfer and PCET reactions, as well as mixed electron-proton vibronic excited states for photoinduced reactions. She is also developing real-time NEO-TDDFT methods and other nonadiabatic dynamics methods for the simulation of ultrafast electronic and nuclear dynamics, targeting applications to photoinduced PCET reactions. She is incorporating these approaches into well-established quantum chemistry software packages and is creating tutorials to explain how to perform NEO calculations and highlight the unique capabilities of this approach. Furthermore, she is maintaining and enhancing a web site on PCET to convey useful information to the community and to provide valuable 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.