Reformulation of Time-Dependent Density Functional Theory for Nonperturbative Dynamics: The Rabi Oscillation Problem Resolved

Rabi oscillations have long been thought to be out of reach in simulations using time-dependent density functional theory (TDDFT), a prominent symptom of the failure of the adiabatic approximation for nonperturbative dynamics. We present a reformulation of TDDFT which requires response quantities only, thus enabling an adiabatic approximation to predict such dynamics accurately because the functional is evaluated on a density close to the ground state, instead of on the fully nonperturbative density. Our reformulation applies to any real-time dynamics, redeeming TDDFT far from equilibrium. Examples of a resonantly-driven local excitation in a model He atom, and charge-transfer in the LiCN molecule are given.Received 22 April 2024Accepted 18 July 2024DOI:https://doi.org/10.1103/PhysRevLett.133.096401© 2024 American Physical SocietyPhysics Subject Headings (PhySH)