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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.

We extend the Runge-Gross theorem for a very general class of open quantum systems under weak assumptions about the nature of the bath and its coupling to the system. We show that for Kohn-Sham (KS) time-dependent density functional theory, it is possible to rigorously include the effects of the environment within a bath functional in the KS potential. A Markovian bath functional inspired by the theory of nonlinear Schrödinger equations is suggested, which can be readily implemented in currently existing real-time codes. Finally, calculations on a helium model system are presented.