We discuss TD-Split, a recent approach to calculate electron transport in A-+B ? A+B- systems.  The Marcus theory nonadiabatic coupling, J=<fA|H|fB>, is traditionally calculated for large systems using the static DFT or Hartree Fock Hamiltonian of either the separated neutral fragments or the full neutral system.  We advocate instead to calculate the ground-state of the combined charged system, (AB)- , where the transferred electron is completely delocalized, and to calculate the nonadiabatic coupling by a time-dependent excitation energy of the full charged system, (AB)- ? (AB)-*.  Results are shown on pentacene and fullerene systems, where factors of 3-5 higher splittings are often found in TD-Split compared with the static Hamiltonian approach, and the tunneling splitting decays much more gently with fragment distance.  TD-Split is a linear response approach so it is suitable both for existing packages as well as real-time and real-time linear-response simulations.

TD-Split: Non-adiabatic splitting from a time-dependent linear response excitation of a delocalized ground-state

243rd National Meeting (2012)

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