The electromagnetic vacuum enhances infrared photodissociation under strong light-matter coupling

Johan Triana Universidad Católica del Norte

Vibrational light-matter coupling is currently one of the most studied research topics due to the unexpected modifications of chemical reaction rates and branching ratios at room temperature. Most heoretical efforts are mainly focused on describing previous experimental measurements in the many-body regime [1], which opens a great opportunity to explore the single-molecule scenario in the full quantum regime [2]. We study the photodissociation dynamics of a single molecular mode coupled to an infrared electromagnetic vacuum in the vibrational strong light-matter coupling for two driven scenarios, i) molecule-driving [] and ii) nanocavity-driving [] (see figure).

We show a significant enhancement of intracavity dissociation probabilities relative to free space scenarios for the same laser intensities. Similar dissociation probabilities are obtained for the cavity-driving scenario with much lower laser intensities than the implemented in the molecule-driving case [3]. Results are based on the modified ladder climbing process in the polariton quasi-continuum below the dissociation threshold, in comparison with the energy levels scheme of a single anharmonic mode [4]. Our work extends the tools to control dissociation yields of small molecules in confined infrared electromagnetic environments.

[1] W. Ahn, J.F. Triana, F. Recabal, F. Herrera and B. Simpkins, Science 380, 1165 (2023). [2] F. Herrera, J. Owrutsky. The Journal of Chemical Physics, 152, 100902 (2020). [3] J.F. Triana, F. Herrera, In preparation (2024). [4] B. Carmeli, A. Nitzan. The Journal of Chemical Physics, 72, 2070 (1980).