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

JOHANNA I FUKS; PETER ELLIOT; ANGEL RUBIO; NEEPA T. MAITRA

JOURNAL OF PHYSICAL CHEMISTRY

AMER CHEMICAL SOC

Lugar: Washington; Año: 2013 vol. 4

0022-3654

We show that whenever an electron transfersbetween closed-shell molecular fragments, the exact correlationpotential of time-dependent density functional theory develops astep and peak structure in the bonding region. This structure has adensity dependence that is nonlocal both in space and in time thateven the exact adiabatic ground-state exchange−correlationfunctional 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 todevelop these structures leads to inaccurate charge-transfer dynamics. This is illustrated by the complete lack of Rabi oscillationsin the dipole moment under conditions of resonant charge transfer for a