Ab-initio Quantum Electrodynamics Approaches to Investigate Polariton Chemistry in the Collective Coupling Regime
Abstract
Coupling electronic states with the quantized radiation field inside an optical cavity creates collective and delocalized excitations of light and matter, referred to as the upper and lower polariton states. These polariton states have delocalized excitations among molecules and the cavity mode, which have been shown to facilitate new chemical reactivities. Thus, polariton chemistry provides a new strategy to control chemical reactivities in a general way by tuning the fundamental properties of photons and provides a new paradigm for enabling chemical transformations that can profoundly impact catalysis, energy production, and the field of chemistry at large. Theoretical investigations play a crucial role in understanding the new principles in this emerging field. Simulating the time-dependent polariton quantum dynamics of such hybrid matter-field systems is a necessary and essential task, as these polariton photochemical reactions often involve a complex dynamical interplay among the electronic, nuclear, and photonic degrees of freedoms (DOFs). However, accurately and efficiently simulating the polaritonic quantum dynamics remains a major challenge and is beyond the paradigm of photochemistry which does not include quantized photons, or quantum optics which does not have a well-defined theory to include the influence of nuclear vibrations. We propose to develop a set of general and powerful theoretical and computational tools that enable direct ab-initio on-the-fly simulations of polariton photochemical processes based on the rigorous QED description of molecule-cavity interactions. Our proposed developments will be based on using rigorous Quantum Electrodynamics theory to describe many molecules coupled to an optical cavity, combined with the efficient and accurate polaritonic structure theory.
Document Details
- Document Type
- DoD Grant Award
- Publication Date
- Mar 06, 2024
- Source ID
- FA95502310438
Entities
People
- Pengfei Huo
Organizations
- Air Force Office of Scientific Research
- United States Air Force
- University of Rochester