A versatile platform for gas-phase molecular polaritonics

Abstract

Strong cavity coupling of gas-phase molecules will enable studies of benchmark chemical processes under strong light-matter interactions with a high level of experimental control and no solvent effects. We recently demonstrated the formation of gas-phase molecular polaritons by strongly coupling the bright ${\nu }_3$, $J=3\to 4$ rovibrational transitions of methane (CH${}_4$) to a Fabry-Pérot optical cavity mode inside a cryogenic buffer gas cell. Here, we further explore the flexible capabilities of this infrastructure. We show that we can greatly increase the collective coupling strength of the molecular ensemble to the cavity by increasing the intracavity CH${}_4$ number density. In doing so, we can tune from the single-mode coupling regime to the multimode coupling regime in which many nested polaritonic states arise as the Rabi splitting approaches the cavity mode spacing. We explore polariton formation for cavity geometries of varying length, finesse, and mirror radius of curvature. We also report a proof-of-principle demonstration of rovibrational gas-phase polariton formation at room temperature. This experimental flexibility affords a great degree of control over the properties of molecular polaritons and opens up a wider range of simple molecular processes to future interrogation under strong cavity-coupling. We anticipate that ongoing work in gas-phase polaritonics will facilitate convergence between experimental results and theoretical models of cavity-altered chemistry and physics.

References in corpus (18)

• Molecular polaritons for controlling chemistry with quantum optics
• Multiple Rabi Splittings under Ultra-Strong Vibrational Coupling
• Molecular polaritonics: Chemical Dynamics under strong Light-Matter Coupling
• Continuous probe of cold complex molecules with infrared frequency comb spectroscopy
• Tuning the coherent propagation of organic exciton-polaritons through dark state delocalization
• Catalysis by Dark States in Vibropolaritonic Chemistry
• Quantum state resolution of the C${}_{60}$ fullerene
• Beyond Strong Coupling in a Massively Multimode Cavity
• Swinging between shine and shadow: Theoretical advances on thermally-activated vibropolaritonic chemistry (a perspective)
• Rovibrational Polaritons in Gas-Phase Methane
• Collective strong coupling in multimode cavity QED
• Nonequilibrium effects of cavity leakage and vibrational dissipation in thermally-activated polariton chemistry
• Ultrafast dynamics of CN radical reactions with chloroform solvent under vibrational strong coupling
• Coupling and Decoupling of Polaritonic States in Multimode Cavities
• Nonadiabatic phenomena in molecular vibrational polaritons
• Cavity-induced Non-Adiabatic Dynamics and Spectroscopy of Molecular Rovibrational Polaritons studied by Multi-Mode Quantum Models
• Multi-normal-mode splitting of a cavity in the presence of atoms -- towards the superstrong coupling regime
• Collective strong coupling in a lossy optical cavity

Cited by in corpus (9)

• When do molecular polaritons behave like optical filters?
• More than just smoke and mirrors: Gas-phase polaritons for optical control of chemistry
• Molecular Polarizability under Vibrational Strong Coupling
• Unraveling Abnormal Collective Effects via the Non-Monotonic Number Dependence of Electron Transfer in Confined Electromagnetic Fields
• A Cavity-Enhanced Spectroscopist's Lens on Molecular Polaritons
• Ab initio study on the dynamics and spectroscopy of collective rovibrational polaritons
• Interplay between Static and Dynamic Disorder: Contrasting Effects on Dark State Population inside a Cavity
• Polaritonic control of blackbody infrared radiative dissociation
• Direct readout of excited state lifetimes in chlorin chromophores under electronic strong coupling