Simulations of Photochemistry Inside An Optical Resonator

Photochemistry has opened the door to new materials and new fabrication processes. However, accurate descriptions of their underlying photophysical properties and mechanisms are necessary to systematically improve designs and fabrication processes. Providing such descriptions remains an open challange. These photophysical properties and mechanisms inherently arise from the simultaneous coupling of quantized nuclear, electronic, and photonic degrees of freedom (DoF), for which there are no analytical solutions except in the simplest of cases.

The goal of this project is to create a publically available computational tool that can perform molecular dynamics (MD) within a Fabry-Pérot cavity while coupling the quantized electronic and photonic DoF. The electric dipole Hamiltonian is used perturbatively to capture this coupling under the framework of density functional theory. This allows for electronic transitions to occur "on-the-fly" during MD trajectories. The first model tested is H₂⁺. Upon accurate reproduction of experimental photodissociation data, HF will be simulated. This will introduce asymmetry and far greater electronic complexity without moving beyond a diatomic molecule, and the plethora of data on HF will allow for the expansion of characteristics to be validated. Upon satisfactory performance with HF, various molecules with more than two atoms will be modeled to attempt simulations of laser chemical vapor deposition, exciton-polaritons, photovoltaics, etc.