Physical Review Letters · 2017 · 177 citations · 32 references
Second LawChemistryOptogeneticsMany-molecule Reaction TriggeredPolariton DynamicSingle MoleculePhotophysical PropertyBiophysicsHealth SciencesPhotonicsPhotochemistryPhysicsMechanistic PhotochemistryPhysical ChemistryQuantum ChemistrySupramolecular PhotochemistryPhotochemistry StatesNatural SciencesMultiphoton ProcessHybrid StatesQuantum Biology
The second law of photochemistry states that, in most cases, no more than one molecule is activated for an excited-state reaction for each photon absorbed by a collection of molecules. In this Letter, we demonstrate that it is possible to trigger a many-molecule reaction using only one photon by strongly coupling the molecular ensemble to a confined light mode. The collective nature of the resulting hybrid states of the system (the so-called polaritons) leads to the formation of a polaritonic "supermolecule" involving the degrees of freedom of all molecules, opening a reaction path on which all involved molecules undergo a chemical transformation. We theoretically investigate the system conditions for this effect to take place and be enhanced.
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The Activated Complex in Chemical Reactions
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Molecular Recognition, Chemical Engineering, Catalysis 13 +10