Physics

Molecular vibration

Homogeneous

Polariton

Coupling (piping)

Atomic physics

Chemical physics

Chemistry

Metallurgy

Materials science

Condensed matter physics

Molecule

Molecular physics

Quantum mechanics

Delocalized electron

Thermodynamics

Physical Review Letters

Collective strong coupling between a disordered ensemble of N localized molecular vibrations and a resonant optical cavity mode gives rise to two polariton and N-1≫2 dark modes. Thus, experimental changes in thermally activated reaction kinetics due to polariton formation appear entropically unlikely and remain a puzzle. Here we show that the overlooked dark modes, while parked at the same energy as bare molecular vibrations, are robustly delocalized across ∼2-3 molecules, yielding enhanced channels of vibrational cooling, concomitantly catalyzing a chemical reaction. As an illustration, we theoretically show an ≈50% increase in an electron transfer rate due to enhanced product stabilization. The reported effects can arise when the homogeneous linewidths of the dark modes are smaller than their energy spacings.

Catalysis by Dark States in Vibropolaritonic Chemistry