Charge Transfer from an Aromatic Adsorbate to a SemiconductorTiO2Surface Probed on the Femtosecond Time Scale with Resonant Inelastic X-Ray Scattering

Abstract

The excited state charge transfer dynamics of an aromatic adsorbate to a rutile TiO(2) surface is studied using a core-hole clock (CHC) implementation of resonant inelastic x-ray scattering (RIXS) on the low femtosecond time scale. Comparing the abundance of the elastic and inelastic radiative N 1s core-hole decay channels provides a method for probing ultrafast injection of electrons resonantly excited to unoccupied molecular orbitals that lie above the conduction band of the substrate on the time scale of the core-hole lifetime. The method is analogous to the CHC implementation of resonant photoemission, but in the case of RIXS it is the emitted soft x-ray photons that are measured rather than photoelectrons, leaving the probed molecules in a neutral rather than ionized final state. The results reveal a charge transfer time of 2.8±1.5 fs from the lowest unoccupied molecular orbital +1 state of adsorbed bi-isonicotinic acid to the conduction band of the TiO(2) substrate.