Ultra-fast intramolecular vibronic coupling revealed by RIXS and RPES maps of an aromatic adsorbate on TiO2(110)

Research output: Contribution to journalArticle

Abstract

Two-dimensional resonant inelastic x-ray scattering (RIXS) and resonant photoelectron spectroscopy (RPES) maps are presented for multilayer and monolayer coverages of an aromatic molecule (bi-isonicotinic acid) on the rutile TiO2(110) single crystal surface. The data reveal ultra-fast intramolecular vibronic coupling upon core excitation from the N 1s orbital into the lowest unoccupied molecular orbital (LUMO) derived resonance. In the RIXS measurements, this results in the splitting of the participator decay channel into a purely elastic line which disperses linearly with excitation energy and a vibronic coupling channel at constant emission energy. In the RPES measurements, the vibronic coupling results in a linear shift in binding energy of the participator channel as the excitation is tuned over the LUMO-derived resonance. Localisation of the vibrations on the molecule on the femtosecond time scale results in predominantly inelastic scattering from the core-excited state in both the physisorbed multilayer and the chemisorbed monolayer.

Details

Authors
  • James N. O'Shea
  • Karsten Handrup
  • Robert H. Temperton
  • Andrew J. Gibson
  • Alessandro Nicolaou
  • Nicolas Jaouen
  • John B. Taylor
  • Louise C. Mayor
  • Janine C. Swarbrick
  • Joachim Schnadt
Organisations
External organisations
  • University of Nottingham
  • Aarhus University
  • Synchrotron SOLEIL
Research areas and keywords

Subject classification (UKÄ) – MANDATORY

  • Atom and Molecular Physics and Optics
Original languageEnglish
Article number204705
JournalJournal of Chemical Physics
Volume148
Issue number20
Publication statusPublished - 2018 May 28
Publication categoryResearch
Peer-reviewedYes