posted on 2024-01-31, 05:05authored byNam Vu, Daniel Mejia-Rodriguez, Nicholas P. Bauman, Ajay Panyala, Erdal Mutlu, Niranjan Govind, Jonathan J. Foley
Polariton chemistry has attracted great attention as
a potential
route to modify chemical structure, properties, and reactivity through
strong interactions among molecular electronic, vibrational, or rovibrational
degrees of freedom. A rigorous theoretical treatment of molecular
polaritons requires the treatment of matter and photon degrees of
freedom on equal quantum mechanical footing. In the limit of molecular
electronic strong or ultrastrong coupling to one or a few molecules,
it is desirable to treat the molecular electronic degrees of freedom
using the tools of ab initio quantum chemistry, yielding
an approach we refer to as ab initio cavity quantum
electrodynamics, where the photon degrees of freedom are treated at
the level of cavity quantum electrodynamics. Here, we present an approach
called Cavity Quantum Electrodynamics Complete Active Space Configuration
Interaction theory to provide ground- and excited-state polaritonic
surfaces with a balanced description of strong correlation effects
among electronic and photonic degrees of freedom. This method provides
a platform for ab initio cavity quantum electrodynamics
when both strong electron correlation and strong light–matter
coupling are important and is an important step toward computational
approaches that yield multiple polaritonic potential energy surfaces
and couplings that can be leveraged for ab initio molecular dynamics simulations of polariton chemistry.