Quantum Dynamics Approaches to Simulate Polariton Photochemistry

在化学系化学理论、模型和计算方法项目的支持下，罗彻斯特大学的霍鹏飞正在开发新的理论方法来模拟极化光化学过程的量子动力学。将分子激子耦合到光学腔内的量子化辐射场会产生混合光-物质状态，即所谓的极化子。极化化学有可能为实现化学转化提供一种新的范式。理论研究对于理解这一新兴领域的新知识和基本原理起着至关重要的作用。霍博士和他的团队正致力于开发新的量子动力学方法，以精确和直接地模拟极化光化学过程。利用这些新的理论方法，霍博士和他的团队将研究这种分子-腔混合系统的动力学，以收集有关极化子光化学基本原理的信息。霍博士将继续在罗切斯特市学区为高中生举办“分子世界之旅”暑期学校，旨在激发他们对分子科学的好奇心和热情。霍博士还将与他的同事们合作组织一个新的碲化物极化化学研讨会，该研讨会将汇集实验学家和理论家，交流极化化学的最新科学发现。准确地模拟分子-腔混合系统的非绝热动力学仍然是一个挑战，超出了目前光化学和量子光学的范围。现有的方法通常基于量子光学模型哈密顿量，该模型在强光-物质耦合状态下会分解，或者基于已知缺陷的混合量子-经典（MQC）模拟。为了应对这些挑战，霍博士和他的团队将开发新的非绝热方法，该方法基于严格的量子电动力学哈密顿量，与常用的MQC方法相比，可以提供精确的动力学模拟。霍博士和他的团队还将开发基于准绝热传播方案的新的动态模拟技术，以在现实的分子-腔混合系统中执行从头算极化子非绝热动力学。提出的工作旨在提供一套变革性的理论工具和框架，可以准确地模拟实时极化量子动力学。这些理论研究有可能提供量子光-物质相互作用诱导化学的基础知识，并促进极化化学的新发现，激发利用光子固有量子行为的变革性设计原则。从这项理论工作中获得的这些基础知识和见解有可能对催化、能源生产和整个化学领域产生深远的影响。该奖项反映了美国国家科学基金会的法定使命，并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，被认为值得支持。

With support from the Chemical Theory, Models and Computational Methods program in the Division of Chemistry, Pengfei Huo of the University of Rochester is developing new theoretical approaches to simulate quantum dynamics of polariton photochemical processes. Coupling molecular excitons to a quantized radiation field inside an optical cavity generates hybrid light-matter states, so called polaritons. Polariton chemistry has the potential to provide a new paradigm for enabling chemical transformations. Theoretical investigations play a vital role in understanding new knowledge and basic principles in this emerging field. Dr. Huo and his group are working to develop new quantum dynamics methods for accurate and direct simulations of polariton photochemical processes. With these new theoretical approaches, Dr. Huo and his team will investigate the dynamics of such molecule-cavity hybrid systems to glean information on the basic principles in polariton photochemistry. Dr. Huo will continue his 'Journey to the Molecular World' summer school for high school students in the Rochester City School District, which aims to inspire their curiosity and enthusiasm about molecular science. Dr. Huo will also collaborate with his colleagues to organize a new Telluride workshop on polariton chemistry, which will bring together experimentalists and theorists for exchanging the most recent scientific discoveries in polariton chemistry.Accurately simulating the non-adiabatic dynamics of the molecule-cavity hybrid system remains a challenge and lies beyond the current scope of photochemistry and quantum optics. Existing approaches are often based on quantum optics model Hamiltonians that break down under the strong light-matter coupling regime, or mixed quantum-classical (MQC) simulations that have known deficiencies. To address these challenges, Dr. Huo and his group will develop new non-adiabatic methods that are based on the rigorous quantum electrodynamics Hamiltonian and provide accurate dynamics simulations compared to the commonly used MQC approaches. Dr. Huo and his team will also develop new on-the-fly simulation techniques based on the quasi-diabatic propagation scheme to perform ab-initio polariton non-adiabatic dynamics in realistic molecule-cavity hybrid systems. The proposed work aims to provide a set of transformative theoretical tools and frameworks that can accurately simulate real-time polaritonic quantum dynamics. These theoretical investigations have the potential to provide fundamental knowledge of quantum light-matter-interaction-induced chemistry and facilitate new discoveries in polariton chemistry, inspiring transformative design principles that take advantage of the intrinsic quantum behaviors of photons. Such fundamental knowledge and insight obtained from this theoretical work has the potential to profoundly impact catalysis, energy production, and the field of chemistry at large.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.