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

O'Shea, James N.; Handrup, Karsten; Temperton, Robert H.; Gibson, Andrew J.; Nicolaou, Alessandro; Jaouen, Nicolas; Taylor, John B.; Mayor, Louise C.; Swarbrick, Janine C.; Schnadt, Joachim

Authors

James N. O'Shea

Karsten Handrup

Robert H. Temperton Robert.Temperton@nottingham.ac.uk

Andrew J. Gibson

Alessandro Nicolaou

Nicolas Jaouen

John B. Taylor

Louise C. Mayor

Janine C. Swarbrick

Joachim Schnadt



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 reveals 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 timescale results in predominantly inelastic scattering from the core-excited state in both the physisorbed multilayer and the chemisorbed monolayer.

Journal Article Type Article
Publication Date May 29, 2018
Journal Journal of Chemical Physics
Print ISSN 0021-9606
Electronic ISSN 1089-7690
Publisher AIP Publishing
Peer Reviewed Peer Reviewed
Volume 148
Issue 20
Article Number 204705
APA6 Citation O'Shea, J. N., Handrup, K., Temperton, R. H., Gibson, A. J., Nicolaou, A., Jaouen, N., …Schnadt, J. (2018). Ultra-fast intramolecular vibronic coupling revealed by RIXS and RPES maps of an aromatic adsorbate on TiO2(110). Journal of Chemical Physics, 148(20), doi:10.1063/1.5024862. ISSN 0021-9606
DOI https://doi.org/10.1063/1.5024862
Publisher URL https://aip.scitation.org/doi/10.1063/1.5024862
Copyright Statement Copyright information regarding this work can be found at the following address: http://eprints.nottingh.../end_user_agreement.pdf
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Copyright Statement
Copyright information regarding this work can be found at the following address: http://eprints.nottingham.ac.uk/end_user_agreement.pdf





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