Theory Department
Max Planck Institute of Microstructure Physics
1997    
1998    
1999    
2000    
2001    
2002    
2003    
2004    
2005    
2006    
2007    
2008    
2009    
2010    
2011    
2012    
2013    
2014    
2015    
2016    
2017    
2018    
2019    
2020    
2021    
Fuks, J. I., Elliott, P., Rubio, A., Maitra, N. T.

Dynamics of charge-transfer processes with time-dependent density functional theory
Journal of Physical Chemistry Letters 4, (5),pp 735-739 (2013)
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 openshell 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.

TH-2013-36