The exact forces on classical nuclei in non-adiabatic charge transfer.
The decomposition of electronic and nuclear motion presented in Abedi et al. [Phys. Rev. Lett. 105, 123002 (2010)] yields a time-dependent potential that drives the nuclear motion and fully accounts for the coupling to the electronic subsystem. Here, we show that propagation of an ensemble of independent classical nuclear trajectories on this exact potential yields dynamics that are essentially indistinguishable from the exact quantum dynamics for a model non-adiabatic charge transfer problem. We point out the importance of step and bump features in the exact potential that are critical in obtaining the correct splitting of the quasiclassical nuclear wave packet in space after it passes through an avoided crossing between two Born-Oppenheimer surfaces and analyze their structure. Finally, an analysis of the exact potentials in the context of trajectory surface hopping is presented, including preliminary investigations of velocity-adjustment and the force-induced decoherence effect.
Max-Planck-Institut of Microstructure Physics, Weinberg 2, D-06120 Halle, Germany.
Federica
F
Agostini
Max-Planck-Institut of Microstructure Physics, Weinberg 2, D-06120 Halle, Germany.
Ali
A
Abedi
Max-Planck-Institut of Microstructure Physics, Weinberg 2, D-06120 Halle, Germany.
Yasumitsu
Y
Suzuki
Max-Planck-Institut of Microstructure Physics, Weinberg 2, D-06120 Halle, Germany.
Seung Kyu
SK
Min
Department of Physics and Astronomy, Hunter College and the Graduate Center of the City University of New York, 695 Park Avenue, New York, New York 10065, USA.
Neepa T
NT
Maitra
Max-Planck-Institut of Microstructure Physics, Weinberg 2, D-06120 Halle, Germany.
E K U
EK
Gross