Search for: All records

Abstract Interaction between light and matter results in new quantum states whose energetics can modify chemical kinetics. In the regime of ensemble vibrational strong coupling (VSC), a macroscopic number$$N$$ $N$of molecular transitions couple to each resonant cavity mode, yielding two hybrid light–matter (polariton) modes and a reservoir of$$N-1$$ $N-1$dark states whose chemical dynamics are essentially those of the bare molecules. This fact is seemingly in opposition to the recently reported modification of thermally activated ground electronic state reactions under VSC. Here we provide a VSC Marcus–Levich–Jortner electron transfer model that potentially addresses this paradox: although entropy favors the transit through dark-state channels, the chemical kinetics can be dictated by a few polaritonic channels with smaller activation energies. The effects of catalytic VSC are maximal at light–matter resonance, in agreement with experimental observations. 

In organic microcavities, hybrid light-matter states can form with energies that differ from the bare molecular excitation energies by nearly 1 eV. A timely question, given the recent advances in the development of thermally activated delayed fluorescence materials, is whether strong light-matter coupling can be used to invert the ordering of singlet and triplet states and, in addition, enhance reverse intersystem crossing (RISC) rates. Here, we demonstrate a complete inversion of the singlet lower polariton and triplet excited states. We also unambiguously measure the RISC rate in strongly coupled organic microcavities and find that, regardless of the large energy level shifts, it is unchanged compared to films of the bare molecules. This observation is a consequence of slow RISC to the lower polariton due to the delocalized nature of the state across many molecules and an inability to compete with RISC to the dark exciton reservoir.