Perspective on Many-Body Methods for Molecular Polaritonic Systems

Recent advances in strong light–matter interactions have revealed a wealth of new physical phenomena in molecules embedded in optical cavities, including modified chemical reactivity, altered excitation spectra, and novel quantum correlations. To describe these effects from first-principles, the field of <em>ab initio</em> quantum electrodynamics (QED) has emerged as a compelling extension of quantum chemistry that treats electronic and photonic degrees of freedom on equal footing. In this Perspective, we review the growing landscape of many-body QED methods, including Hartree–Fock, density functional theory (QEDFT), time-dependent DFT (QED-TDDFT), configuration interaction (QED-CI), complete active space (QED-CASSCF), coupled cluster (QED-CC), quantum Monte Carlo (QED-QMC), and density matrix renormalization group (QED-DMRG), highlighting recent developments and implementations. We further explore real-time methods, gradient and Hessian formalisms, and the integration of nonadiabatic nuclear dynamics. Applications range from benchmark simulations of polaritonic chemistry to quantum simulations on emerging quantum hardware. We conclude by outlining future directions for theory development and interdisciplinary efforts at the interface of quantum chemistry, condensed matter, and quantum optics.. Authors: Bauman, Nicholas [Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)]; Cunha, Leonardo A. [Flatiron Institute, New York, NY (United States)] (ORCID:0000000326712375); DePrince, A. Eugene [Florida State Univ., Tallahassee, FL (United States)]; Flick, Johannes [Flatiron Institute, New York, NY (United States); City College of New York, NY (United States)]; Foley, Jonathan J. [Univ. of North Carolina, Charlotte, NC (United States)]. DOE Contract: 89233218CNA000001; AC02-05CH11231; SC0017889; SC0024496. Subjects: Hamiltonians; cavities; molecules; polaritons; quantum mechanics