Going beyond Born-Oppenheimer in TDDFT

PHYS 69

Ali Abedi, abedi@physik.fu-berlin.de, Institut fur Theoretische Physik, Freie Universitaet Berlin, Arnimallee 14, D-14195 Berlin, Berlin, Germany, Neepa T. Maitra, nmaitra@hunter.cuny.edu, Department of Physics and Astronomy, Hunter College of the City University of New York, 695 Park Avenue, New York, NY 10021, and EKU Gross, hardy@physik.fu-berlin.de, Institut fur Theoretische Physik, Freie Universitat Berlin, Arnimallee 14, 12203 Berlin, Germany.
As time-dependent density functional theory (TDDFT) is an ab initio quantum mechanical method that can treat systems with large numbers of electrons efficiently, it is an ideal candidate for use in coupled electron-ion dynamics in photochemical processes. Recently there have been such studies, treating the nuclei classically. Beginning with an exact decomposition of the full electron-ion wavefunction, we discuss an approach which includes ionic quantum effects semiclassically, while maintaining the fully quantum TDDFT approach for electrons. The electronic “back-reaction” on the nuclei is rigorously contained in a time-dependent vector potential. We also discuss a particular fundamental challenge for TDDFT in capturing branching of trajectories.
 

Excited Electronic States in Chemistry and Biology: Theory and Experiment
1:20 PM-4:50 PM, Sunday, August 19, 2007 BCEC -- 160A, Oral

Division of Physical Chemistry

The 234th ACS National Meeting, Boston, MA, August 19-23, 2007