Collective Polaritonic Effects on Chemical Dynamics Suppressed by Disorder

We present a powerful formalism, disordered collective dynamics usingtruncated equations (d-CUT-E), to simulate the ultrafast quantum dynamics ofmolecular polaritons in the collective strong coupling regime, where adisordered ensemble of N≫10^6 molecules couples to a cavity mode.Notably, we can capture this dynamics with a cavity hosting a singleeffective molecule with ∼ N_bins electronic states, whereN_bins≪ N is the number of bins discretizing the disorder distribution.Using d-CUT-E we conclude that strong coupling, as evaluated from linearoptical spectra, can be a poor proxy for polariton chemistry. For highlydisordered ensembles, total reaction yield upon broadband excitation isidentical to that outside of the cavity, while narrowband excitation producesdistinct reaction yields solely due to differences in the initial statesprepared prior to the reaction.