CAREER: Quantum Dynamics of Photochemical Reactions in Solar Energy Conversions

罗切斯特大学的霍鹏飞获得了化学系化学理论、模型和计算方法项目颁发的与太阳能转换相关的理论研究职业奖。霍和他的同事开发了研究光化学反应的新的量子动力学方法。这些反应对太阳能燃料的生产至关重要。在太阳能到燃料的反应中，一个分子被光的吸收所激发，这个过程允许该分子将电子和质子转移到另一个分子。缺乏有效和准确的理论方法，阻碍了对这些反应的定量和预测性理解。霍氏团队开发了新的量子动力学方法，旨在解决这些理论挑战。他们使用计算工具来模拟光催化转化中耦合的电子和质子转移反应。这些见解启发了下一代光催化能源生产的新设计原则和范例。霍建华的研究项目与以理论化学为核心的教育内容相结合，包括罗切斯特市学区为高中生开设的“分子世界之旅”暑期学校。该项目旨在激发学生对分子科学的好奇心和热情，并鼓励高中生继续接受科学、技术、工程和数学方面的高等教育。动态量子动力学模拟是研究非平衡光化学反应的最理想方法之一。由于缺乏有效的量子动力学方法，以及非绝热动力学方法和绝热电子结构计算之间的差异，准确地进行这样的模拟在理论化学中仍然是一个巨大的挑战。为了应对这些长期存在的挑战，霍博士和他的团队正在开发新的路径积分量子动力学方法，这种方法可以准确地模拟非绝热电子跃迁，并通过对所有自由度的经典描述来显式地纳入核量子效应。他们还在开发新的传播方案，使非绝热动力学方法和绝热电子结构计算之间能够实现无缝接口，明确地避免了将非绝热动力学方法重新表述为绝热表示的额外努力。结合上述两种类型的技术，霍组正在进行即时模拟，以研究光致质子耦合电子转移(PI-PCET)反应的基本机制，该反应是许多太阳能转换过程的中心。他的团队正在探索可通过实验测试的机械假说，这些假说利用PI-PCET的非平衡和量子力学性质来实现新的化学反应。这些研究可能会产生一套普遍和广泛适用的理论工具，可以显著扩大量子动力学模拟的范围，并提供基本知识和新的设计原则来预测和控制下一代光催化剂的反应性。这一奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。

Pengfei Huo of the University of Rochester is supported by a CAREER award from the Chemical Theory, Models and Computational Methods program in the Division of Chemistry for theoretical research relevant to solar energy conversion. Huo and coworkers develop new quantum dynamics approaches for investigating photochemical reaction. These reactions are crucial for solar fuel production. In solar-to-fuel reactions, a molecule is excited by absorption of light, and this process allows the molecule to transfer of both electrons and protons to another molecule. A quantitative and predictive understanding of these reactions is hampered by the lack of efficient and accurate theoretical approaches. The Huo group develops new quantum dynamics methods that aim to address these theoretical challenges. They use computational tools to simulate coupled electron and proton transfer reactions in photocatalytic conversions. Such insights inspire new design principles and paradigms for next-generation photocatalytic energy production. Dr. Huo's research program is integrated with an educational component centered on theoretical chemistry, including the 'Journey to the Molecular World' summer school for high school students in the Rochester City School District. This project aims to inspires student curiosity and enthusiasm about molecular science and encourage high school students to pursue higher education in Science, Technology, Engineering, and Mathematics.On-the-fly quantum dynamics simulation is one of the most desirable approaches to investigate non-equilibrium photochemical reactions. Accurately performing such simulations remains a significant challenge in theoretical chemistry, due to a lack of efficient quantum dynamics methods as well as the discrepancy between diabatic dynamics methods and adiabatic electronic structure calculations. To address these long-standing challenges, Dr. Huo and his team are developing new path-integral quantum dynamics approaches that can accurately simulate non-adiabatic electronic transitions and explicitly incorporate nuclear quantum effects through a classical-like description for all degrees of freedom. They are also developing new propagation schemes that enable a seamless interface between diabatic dynamics methods and adiabatic electronic structure calculations, explicitly avoiding additional efforts to reformulate diabatic dynamics methods to the adiabatic representations. Combining the above two types of techniques, the Huo group is performing on-the-fly simulations to investigate the fundamental mechanisms of photoinduced proton-coupled electron transfer (PI-PCET) reactions which are at the center of many solar energy conversion processes. His team is exploring experimentally-testable mechanistic hypotheses that take advantage of the non-equilibrium and quantum mechanical nature of PI-PCET to achieve new chemical reactivities. These investigations may yield a set of general and widely applicable theoretical tools that can significantly expand the scope of quantum dynamics simulations, as well as provide fundamental knowledge and new design principles to predict and control the reactivities of next-generation photocatalysts.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.