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O: Fachverband Oberflächenphysik
O 67: Poster Session V: Ultrafast electron dynamics at surface and interfaces I
O 67.1: Poster
Wednesday, March 3, 2021, 10:30–12:30, P
Improved projection-operator diabatization for electron transfer on periodic surfaces — •Simiam Ghan1, Karsten Reuter1,2, and Harald Oberhofer1 — 1Chair for Theoretical Chemistry, Technical University of Munich, Garching, Germany — 2Fritz Haber Institute of the Max Planck Society, Berlin, Germany
We discuss the recently-proposed[1] projection-operator diabatization method POD2GS for calculating electronic coupling in donor-acceptor charge transfer systems. The new scheme offers accurate electronic couplings by constructing diabats which remain localized on their respective fragments, as demonstrated for the Hab11 benchmark suite with molecular dimers.
Here, we apply this improved scheme to explore electron transfer from photoexcited adsorbates to surfaces, a problem for which the original POD method has been widely used. Specifically, we report results for the case of monolayers of core-hole excited Argon on ferromagnetic substrates, where accurate spin-dependent electron transfer lifetimes have been measured experimentally. Aspects of periodic boundary conditions in the electron transfer model are discussed; in particular, we examine the validity of the Γ-point approximation which is commonly used with POD models for electron transfer on surfaces.
[1] S. Ghan et al., J. Chem. Theory Comput. 16, 7431 (2020).