Freezing molecules with light: How long can one maintain a non-equilibrium molecular geometry by strong light-matter coupling?

Abstract: In molecular photochemistry, the non-equilibrium character and subsequent ultrafast relaxation dynamics of photoexcitations near the Franck-Condon region limit the control of their chemical reactivity. We address how to harness strong light-matter coupling in optical microcavities to isolate and preferentially select specific reaction pathways out of the myriad of possibilities present in large-scale complex systems. Using Fermi's Golden Rule and realistic molecular parameters, we estimate the extent to which molecular configurations can be "locked" into non-equilibrium excited state configurations for timescales well beyond their natural relaxation times. For upper polaritons--which are largely excitonic in character, molecular systems can be locked into their ground state geometries for tens to thousands of picoseconds and varies with the strength of the exciton/phonon coupling (Huang-Rhys parameter). On the other hand, relaxed LP lifetimes are nearly uniformly distributed between 2.1-2.4\,ps and are nearly independent of the Huang-Rhys parameter.