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 of molecular transitions couple to each resonant cavity mode, yielding two hybrid light–matter (polariton) modes and a reservoir of 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.
Highlights
Interaction between light and matter results in new quantum states whose energetics can modify chemical kinetics
Where JRP is the non-adiabatic coupling between electronic states, λS is the outer-sphere reorganization energy related to the lowfrequency degrees of freedom of the solvent, ωP is the frequency of a high-frequency intramolecular mode with quantum number labeled by v, S 1⁄4 λP=hωP is a Huang–Rhys parameter with λP the reorganization energy of the quantum mode, ΔE is the difference in energy between the equilibrium configurations of the R and P potential energy surfaces, and kB is the Boltzmann constant
We have shown that vibrational strong coupling (VSC) can result in catalysis of thermally activated (TA) reactions
Summary
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 of molecular transitions couple to each resonant cavity mode, yielding two hybrid light–matter (polariton) modes and a reservoir of N À 1 dark states whose chemical dynamics are essentially those of the bare molecules. It is important to highlight that the VSC in these samples is the consequence of an ensemble effect: each cavity mode (i.e., resonant with the polarization of the material) coherently couples to a large number of molecules This coupling leads to two polaritonic modes and a macroscopic set of quasidegenerate dark (subradiant) modes that, to a good approximation, should feature chemical dynamics that is indistinguishable from that of the bare molecular modes[16]. We believe that this mechanism of polaritonic activation barrier reduction might be a widespread feature among such processes
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