When molecular transitions strongly couple to photon modes, they form hybrid light-matter modes called polaritons. While collective vibrational strong coupling is a promising avenue for control of chemistry, it can be deterred by the large number of quasi-degenerate dark modes. The macroscopic occupation of a single polariton mode by excitations, as observed in Bose-Einstein condensation, offers promise for overcoming this issue. The hybrid nature of polaritons allows them to exhibit phenomena like Bose-Einstein condensation at room temperature due to their photonic component while also affecting molecular processes, like chemical reactions. Here we theoretically investigate the effect of vibrational polariton condensation on the kinetics of electron transfer processes. Compared with excitation with infrared laser sources, the condensate changes the reaction yield significantly due to additional channels with reduced activation barriers resulting from the large accumulation of energy in the lower polariton, and the many modes available for energy redistribution during the reaction. Our results offer tantalizing opportunities to use condensates for driving chemical reactions, kinetically bypassing usual constraints of fast intramolecular vibrational redistribution in condensed phase.

Driving chemical reactions with polariton condensates

ACS Spring 2022

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