Enhanced optical nonlinearities under strong light-matter coupling

Abstract

Optical microcavities and metallic nanostructures have been shown to significantly modulate the dynamics and spectroscopic response of molecular systems. We present a study of the nonlinear optics of a model consisting of $N$ anharmonic multilevel systems (e.g., Morse oscillators) undergoing collective strong coupling with a resonant infrared microcavity. We find that, under experimentally accessible conditions, molecular systems in microcavities may have nonlinear phenomena significantly intensified due to the high quality of polariton resonances and the enhanced microcavity electromagnetic energy density relative to free space. Particularly large enhancement of multiphoton absorption happens when multipolariton states are resonant with bare molecule multiphoton transitions. In particular, our model predicts two-photon absorption cross section enhancements by several orders of magnitude relative to free space when the Rabi splitting ${\Omega }_R$ is approximately equal to the molecular anharmonic shift $2\Delta$. Our results provide rough upper bounds to resonant nonlinear response enhancement factors as relaxation to dark states is treated phenomenologically. Notably, ensembles of two-level systems undergoing strong coupling with a cavity (described by the Tavis-Cummings model) show no such optical nonlinearity enhancements, highlighting the rich phenomenology afforded by multilevel anharmonic systems. Similar conclusions are expected to hold for excitonic systems that share features with our model (e.g., molecular dyes with accessible S_0 -> S_1 -> S_2 transitions) and strongly interact with a UV-visible cavity.

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• Strong coupling in chiral cavities: nonperturbative framework for enantiomer discrimination
• Polariton relaxation under vibrational strong coupling: Comparing cavity molecular dynamics simulations against Fermi's golden rule rate
• Energy-efficient pathway for selectively exciting solute molecules to high vibrational states via solvent vibration-polariton pumping
• Generalization of the Tavis-Cummings model for multi-level anharmonic systems: insights on the second excitation manifold
• QM/MM Modeling of Vibrational Polariton Induced Energy Transfer and Chemical Dynamics
• When do molecular polaritons behave like optical filters?
• Polaron-enhanced polariton nonlinearity in lead halide perovskites
• An efficient and flexible approach for computing rovibrational polaritons from first principles
• Cavity Induced Collective Behavior in the Polaritonic Ground State
• Selective Excitation of IR-Inactive Modes via Vibrational Polaritons: Insights from Atomistic Simulations
• Disentangling collective coupling in vibrational polaritons with double quantum coherence spectroscopy
• The role of dark polariton states for electronic strong coupling in molecules
• Ab initio study on the dynamics and spectroscopy of collective rovibrational polaritons
• Degenerate parametric down-conversion facilitated by exciton-plasmon polariton states in nonlinear plasmonic cavity
• Nonlinear opto-vibronics in molecular systems
• Deterministic Shaping of Quantum Light Statistics