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Title: Charge transfer interactions of a Ru(II) dye complex and related ligand molecules adsorbed on Au(111)

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.3656682· OSTI ID:22038747
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  1. School of Physics and Astronomy, University of Nottingham, Nottingham NG7 2RD (United Kingdom)

The interaction of the dye molecule, N3 (cis-bis(isothiocyanato)bis(2,2{sup '}-bipyridyl-4,4{sup '}-dicarboxylato) -ruthenium(II)), and related ligand molecules with a Au(111) surface has been studied using synchrotron radiation-based electron spectroscopy. Resonant photoemission spectroscopy (RPES) and autoionization of the adsorbed molecules have been used to probe the coupling between the molecules and the substrate. Evidence of charge transfer from the states near the Fermi level of the gold substrate into the lowest unoccupied molecular orbital (LUMO) of the molecules is found in the monolayer RPES spectra of both isonicotinic acid and bi-isonicotinic acid (a ligand of N3), but not for the N3 molecule itself. Calibrated x-ray absorption spectroscopy and valence band spectra of the monolayers reveals that the LUMO crosses the Fermi level of the surface in all cases, showing that charge transfer is energetically possible both from and to the molecule. A core-hole clock analysis of the resonant photoemission reveals a charge transfer time of around 4 fs from the LUMO of the N3 dye molecule to the surface. The lack of charge transfer in the opposite direction is understood in terms of the lack of spatial overlap between the {pi}*-orbitals in the aromatic rings of the bi-isonicotinic acid ligands of N3 and the gold surface.

OSTI ID:
22038747
Journal Information:
Journal of Chemical Physics, Vol. 135, Issue 16; Other Information: (c) 2011 American Institute of Physics; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
Country of Publication:
United States
Language:
English