We present an approach to finding the transit time for the flow of an electron between spatially localized orbitals, which we term the 'electron orbital-occupancy problem'.  The time dependence of the electron orbital-occupancy is investigated by initially localizing an electron in one atomic orbital and following the time development of the corresponding non-stationary wavefunction of the time-independent Hamiltonian as the electron travels to a second orbital. The transition time is then extracted from the time-dependent orbital occupancy through the application of conditional probability analysis with a minimum flow rate.  Unlike approaches based on simple probability analysis, this approach yields electron transit-time probabilities that converge as the time-step used in the simulations is decreased. The method is demonstrated on cases of two-state oscillations.

Characterizing the time development of electron orbital occupancy: Application to two state oscillations

244th National Meeting (2012)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.