Chemical reactivity under collective vibrational strong coupling

Area of Science:

• Quantum Chemistry
• Chemical Physics
• Cavity Quantum Electrodynamics

Background:

• Experiments show optical cavities can alter chemical reactions, but theoretical understanding, especially resonant effects in the collective limit, is limited.
• The interaction between collective molecular vibrations and optical cavity modes is an active area of research.

Purpose of the Study:

• To theoretically investigate unimolecular dissociation reactions of molecules interacting with an infrared optical cavity mode.
• To understand the role of collective vibrational strong coupling in modifying reaction rates.

Main Methods:

• Theoretical study of unimolecular dissociation reactions.
• Analysis of collective interaction via vibrational dipole moments.
• Numerical simulations for up to 10^4 molecules.

Main Results:

• Reaction rates can decrease with an increasing number of aligned molecules when the cavity is resonant with molecular vibrational modes.
• A scaling relation based on collective Rabi splitting predicts the onset of reaction rate modification.
• Demonstrated effects of collective vibrational strong coupling on reaction dynamics.

Conclusions:

• Collective vibrational strong coupling in optical cavities offers a pathway to control chemical reaction rates.
• The findings provide a theoretical framework and predictive tool for cavity-controlled chemistry.