Excitonic Bloch equations from first principles

The ultrafast conversion of coherent excitons into incoherent excitons, as well as the subsequent exciton diffusion and thermalization, are central topics in current scientific research due to their relevance in optoelectronics, photovoltaics and photocatalysis. Current approaches to the exciton dynamics rely on model Hamiltonians that depend on already screened electron-electron and electron-phonon couplings. In this work, we subject the state-of-the-art methods to scrutiny using the ab initio Hamiltonian for electrons and phonons. We offer a rigorous and intuitive proof demonstrating that the exciton dynamics governed by model Hamiltonians is affected by an overscreening of the electron-phonon interaction. The introduction of an auxiliary exciton species, termed the irreducible exciton, enables us to formulate a theory free from overscreening and derive the excitonic Bloch equations. These equations describe the time-evolution of coherent, irreducible, and incoherent excitons during and after the optical excitation. They are applicable beyond the linear regime, and predict that the total number of excitons is preserved when the external fields are switched off.