Electronic rearrangement in a photoexcited atomic cluster adsorbed on a surface involves many coupled electronic states of both cluster and substrate. Coupling of electronic transitions in the cluster with electronic density fluctuations and atomic vibrations in the substrate leads to a dissipative dynamics of electron transfer, electronic relaxation, and electronic photomobilies. A consistent treatment of medium effects is obtained within a statistical density matrix approach and partitioning of the total system into primary and secondary regions. Derived equations of motion for reduced density matrices can be solved using basis sets of orbitals generated by ab initio density functionals provided they generate correct electronic density of states. A combined reduced density matrix – ab initio dynamics method has been developed and applied to the photoinduced electronic dynamics of silver atomic clusters adsorbed on silicon and on titanium dioxide semiconductor surfaces, and examples will be shown of results obtained for electron transfer, relaxation, and mobilities at the surfaces, in work done in collaboration with T. Vazhappilly, R. Hembree, D. Kilin, and M. P. deLara-Castells. These phenomena are all relevant to the development of new materials for photovoltaic and photoelectrochemical devices.<br/>

Combined reduced density matrix: ab initio electronic treatment and applications to the photoinduced dissipative dynamics of atomic clusters adsorbed on semiconductor surfaces

2019 Spring National Meeting

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