Charge transfer in time-dependent density-functional theory: Insights from the asymmetric Hubbard dimer

Abstract

We show that propagation with the best possible adiabatic approximation in time-dependent density-functional theory fails to properly transfer charge in an asymmetric two-site Hubbard model when beginning in the ground state. The approximation is adiabatic but exact otherwise, constructed from the exact ground-state exchange-correlation functional that we compute via constrained search. The model shares the essential features of charge-transfer dynamics in a real-space long-range molecule, so the results imply that the best possible adiabatic approximation, despite being able to capture nonlocal ground-state step features relevant to dissociation and charge-transfer excitations, cannot capture fully time-resolved charge-transfer dynamics out of the ground state.