Modification of chemical reactivity via light–matter coherence

Experimental evidence of chemical reactivity in cavity quantum electrodynamics shows modifications of reaction rates under strong light-matter coupling in contrast with out-of-cavity scenario [1,2]. However, the development of general theories to understand and reproduce experimental measurements remains a challenge. We propose a quantum mechanical model that describes the reaction-rate suppression of up to 80% observed in experiments of phenyl isocyanate alcoholysis with cyclohexanol in a Fabry-Perot cavity [3]. We implement a Lindblad quantum master equation that describes the reactive vibrational NCO mode for an ensemble of phenyl isocyanate molecules coupled to a resonant electromagnetic cavity vacuum. Rate suppressions are predicted as a consequence of the resonant depopulation of the reactive vibrational mode, relative to a canonical Boltzmann distribution. We show that energetic disorder protects the light-matter coherences of an ensemble of molecules from many-body dilution of correlations, in agreement with recent work on disorder-assisted entanglement protection [4]. Our findings extend the understanding of cavity-modified chemistry and suggests connections with quantum science that have yet to be explored.

[1] F. Herrera & J. Owrutsky, J. Chem. Phys., 152(10) (2020).

[2] J. A. Hutchison, et al., Angew. Chem., 51(7), 1592-1596 (2012).

[3] W. Ahn, et al., Science, 380(6650), 1165-1168 (2023).

[4] D. Wellnitz, et. al., Commun. Phys., 5(1), 120 (2022).