Theoretical and Experimental Investigations of Gas-Phase Molecular Polaritons
Abstract
The primary goal of this project is to investigate gas-phase molecular polaritonic systems under electronic strong coupling through a combination of new theoretical ab initio methods and the establishment of an experimental platform. Polaritons, which are hybrid light-matter states induced by strong coupling between light and matter, have been found to alter chemical reactivity. Therefore, gaining a better understanding of polaritons opens new possibilities for controlling chemical reactions using light. Despite extensive recent efforts, theoretical approaches for describing and experimental platforms for controlling gas-phase molecular polaritonic systems are still in their early stages. Advancements necessary for polaritons to realize their full potential of controlling chemical reactivity are the primary objective of this project. Quantum electrodynamics coupled-cluster (QED-CC) approaches have been introduced to theoretically describe polaritonic systems. However, all currently existing implementations have only included a maximum of double electronic excitation in the cluster operator, which is likely to limit their accuracy. Leveraging our expertise in a related set of CC methods called multicomponent CC theory, this project will implement contributions from connected electronic triple excitations for this first time. Similar to the familiar CCSD(T) method, the methods introduced in the project will be the gold standard ab initio methods for polaritonic chemistry. We have also developed a unique instrument coupling a dense, low temperature Laval flow with cavity ringdown spectroscopy (CRDS) in the near-IR. Our recent experiments on CN have suggested the onset of electronic strong coupling, which is supported by previous suggestions in the literature that CRDS experiments could be used to investigate polaritonic systems. Our goal is to identify clear signatures of electronic strong coupling in this experiment. Finally, we will pursue effects on the reaction dynamics of formaldehyde that are altered due to polariton formation. QED-CC calculations will be used to validate these experiments.
Document Details
- Document Type
- DoD Grant Award
- Publication Date
- Feb 06, 2025
- Source ID
- FA95502410199
Entities
People
- Kurt Brorsen
Organizations
- Air Force Office of Scientific Research
- Office of the Secretary of Defense
- University of Missouri System