Time-dependent exchange-correlation functional for a Hubbard dimer: Quantifying nonadiabatic effects

We address and quantify the role of nonadiabaticity (“memory effects”) in the exchange-correlation (xc) functional of time-dependent density functional theory (TDDFT) for describing nonlinear dynamics of many-body systems. Time-dependent resonant processes are particularly challenging for available TDDFT approximations, due to their strong nonlinear and nonadiabatic character. None of the known approximate density functionals are able to cope with this class of problems in a satisfactory manner. In this work we look at the prototypical example of the resonant processes by considering Rabi oscillations within the exactly soluble two-site Hubbard model. We construct the exact adiabatic xc functional and show that (i) it does not reproduce correctly resonant Rabi dynamics, and (ii) there is a sizable nonadiabatic contribution to the exact xc potential, which turns out to be small only at the beginning and at the end of the Rabi cycle when the ground-state population is dominant. We then propose a “two-level” approximation for the time-dependent xc potential which can capture Rabi dynamics in the two-site problem. It works well both for resonant and for detuned Rabi oscillations and becomes essentially exact in the linear response regime.
We acknowledge financial support from the European Research Council Advanced Grant DYNamo (Grant No. ERC-2010-AdG-267374), Spanish Grant (Grant No. FIS2010-21282-C02-01), Grupos Consolidados UPV/EHU del Gobierno Vasco (Grant No. IT578-13), and Ikerbasque and the European Commission projects CRONOS (Grant No. 280879-2 CRONOS CP-FP7).