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Abstract

Charge transfer pathways and charge transfer times in molecular films and in adsorbate layers depend both on the details of the electronic structure as well as on the degree of the initial localization of the propagating excited electronic state. For C₆F₆ molecular adsorbate films on the Cu(111) surface we determined the interplay between excited state localization and charge transfer pathways. In particular we selectively prepared a free-particle-like LUMO band excitation and compared it to a molecularly localized core-excited C1s → π⁎ C₆F₆ LUMO state using time-resolved two-photon photoemission (tr-2PPE) and core–hole–clock (CHC) spectroscopy, respectively. For the molecularly localized core-excited C1s → π⁎ C₆F₆ LUMO state, we separate the intramolecular dynamics from the charge transfer dynamics to the metal substrate by taking the intramolecular dynamics of the free C₆F₆ molecule into account. Our analysis yields a generally applicable description of charge transfer within molecular adsorbates and to the substrate.