First-principles molecular quantum electrodynamics theory at all coupling strengths

Abstract

The ever-growing intersection of quantum electrodynamics (QED) and molecular processes has shown remarkable and unanticipated advancements in altering molecular properties and reactivity by exploiting light-matter couplings. In recent years, multiple ab initio methods have been developed to compute the eigenstates of molecular systems strongly coupled to cavities, ranging from the mean-field to quantum many-body methods. The quantum many-body methods, such as coupled-cluster theories, usually rely on the quality of mean-field reference wavefunctions. Hence, developing efficient and physically reliable mean-filed approaches for molecular quantum electrodynamics problems is crucial. The current widely used methods, such as QED Hartree-Fock and the self-consistent counterpart, are limited to specific coupling regimes. In this work, we developed a variational transformation-based molecular quantum electrodynamics mean-field method, namely VT-QEDHF, for light-matter interaction at arbitrary coupling strength. The numerical benchmark demonstrates that the VT-QEDHF method naturally connects both QEDHF and self-consistent QEDHF methods at the two limits, showcasing the advantage of VT-QEHDF across all coupling strengths.