PNNL

Abstract

Strong light–matter coupling in optical cavities enables the manipulation of chemical and physical properties without altering molecular composition. Theoretical modeling of such phenomena requires exchange-correlation (XC) functionals that account for both electron–electron and electron–photon (ep) interactions within quantum electrodynamical density functional theory (QEDFT). In this work, we develop a meta-generalized gradient approximation (meta-GGA) specifically targeting the cavity-dependent XC interaction in strongly coupled light–matter systems. This novel approximation is built upon a new semilocal polarizability approximation, which draws from the jellium with- a-gap model, and can be extended to a “global hybrid” variant that goes beyond the isotropic model from previous approximations. The polarizability model yields significantly improved dispersion coefficients and benchmark calculations with the cavity dependent XC functional demonstrate improved agreement with QED Hartree-Fock (QED-HF) reference energies. Application to the regioselectivity of brominated nitrobenzene intermediates reveals the functional’s capacity to capture cavity-induced energetic shifts. Our results advance the Jacob’s ladder of functionals for QEDFT and provide a practical tool for modeling polaritonic chemistry.