Modifying the Nonradiative Decay Dynamics through Conical Intersections via Collective Coupling to a Cavity Mode

Area of Science:

• Physical Chemistry
• Quantum Optics
• Spectroscopy

Background:

• Coupling molecular ensembles to microcavity electromagnetic modes alters molecular photophysics and photochemistry.
• Understanding these light-matter interactions is crucial for controlling chemical reactions at the molecular level.

Purpose of the Study:

• Investigate how collective coupling effects modify photochemical mechanisms and rates.
• Examine photodissociation in NaI and nonradiative decay in pyrazine within a microcavity.

Main Methods:

• Direct excitation into lower and upper polaritonic states.
• Analysis of molecular dynamics in coupled light-matter hybrid states.
• Studying the effect of nonreactive buffer molecules on photochemical processes.

Main Results:

• Excitation into lower polaritonic states yields dynamics similar to isolated molecules.
• Upper polaritonic state excitation leads to complex dynamics involving dark states and delayed photochemical processes.
• A buffer of nonreactive molecules effectively delays photochemical reactions in the ensemble.

Conclusions:

• Microcavity coupling significantly alters molecular photochemical dynamics, especially when exciting upper polaritonic states.
• This approach offers a method to control and delay photochemical reactions, with potential applications in chemical synthesis and control.