Theory of excitonic polarons: From models to first-principles calculations

Excitons are neutral excitations that are composed of electrons and holes bound together by their attractive Coulomb interaction. The electron and the hole forming the exciton also interact with the underlying atomic lattice, and this interaction can lead to a trapping potential that favors exciton localization. The quasiparticle thus formed by the exciton and the surrounding lattice distortion is called excitonic polaron. Excitonic polarons have long been thought to exist in a variety of materials, and are often invoked to explain the Stokes shift between the optical absorption edge and the photoluminescence peak. However, quantitative ab initio calculations of these effects are exceedingly rare. In this manuscript, we present a theory of excitonic polarons that is amenable to first -principles calculations. We first apply this theory to model Hamiltonians for Wannier excitons experiencing Frohlich or Holstein electron -phonon couplings. We find that, in the case of Frohlich interactions, excitonic polarons only form when there is a significant difference between electron and hole effective masses. Then, we apply this theory to calculating excitonic polarons in lithium fluoride ab initio. The key advantage of the present approach is that it does not require supercells, therefore it can be used to study a variety of materials hosting either small or large excitonic polarons. This work constitutes the first step toward a complete ab initio many -body theory of excitonic polarons in real materials.