Cavity Controlled Molecular Photo-physics
Figure 1. Schematic showing how molecular polaritons form from the strong coupling of cavity photons and molecular electronic transitions.
When strong enough, the interaction of light and matter causes the formation of hybridized states known as polaritons, as shown at left. This process is directly analogous to formation of molecular orbitals from the hybridization of atomic electronic states.
In contrast to their well-studied atomic counterparts, polariton formation using complex molecules creates new, unexplored energy landscapes on which the correlated roles of electrons, nuclei, and photons drive properties important for technological applications.
One class of open questions in the structure-property relationships central to the application of molecular polaritons in technologies relates to ways equilibrium molecular geometry changes upon polariton formation. One such proposal is shown at right. To answers these questions, we are developing and using Raman spectroscopy to detail changes in electronic potential energy surfaces following polariton formation and excitation.
Figure 2. Comparison of excited state potential energy surfaces of molecules in free space (left panel) and strongly coupled to the photons of a micro-cavity (right panel).
Representative publications:
1) 'Local molecular probes of ultrafast relaxation in strongly coupled metalloporphyrin-cavity systems.' Aleksandr G. Avramenko and Aaron S. Rury, The Journal of Chemical Physics, 155, 064702, (2021)
2) 'Quantum Control of Ultrafast Internal Conversion using Nanoconfined Virtual Photons', Aleksandr G. Avramenko and Aaron S. Rury, The Journal of Physical Chemistry Letters, 2020, 11, pp 1013-1021
3) 'Interrogating the Structure of Molecular Cavity Polaritons with Resonance Raman Scattering: An Experimentally Motivated Theoretical Description', Aleksandr G. Avramenko and Aaron S. Rury, The Journal of Physical Chemistry C, 2019, 123, pp 30551-30561