Dynamics of Charge-Transfer Processes with Time-Dependent Density Functional Theory.

Abstract

We show that whenever an electron transfers between closed-shell molecular fragments, the exact correlation potential of time-dependent density functional theory develops a step and peak structure in the bonding region. This structure has a density dependence that is nonlocal both in space and in time that even the exact adiabatic ground-state exchange-correlation functional fails to capture it. For charge-transfer between open-shell fragments, an initial step and peak vanish as the charge-transfer state is reached. The inability of usual approximations to develop these structures leads to inaccurate charge-transfer dynamics. This is illustrated by the complete lack of Rabi oscillations in the dipole moment under conditions of resonant charge transfer for an exactly solvable model system. The results transcend the model and are applicable to more realistic molecular complexes.