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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

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


Authors

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JAMES O'SHEA J.OSHEA@NOTTINGHAM.AC.UK
Associate Professor and Reader in Physics

Karsten Handrup

Robert H. Temperton

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.

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), Article 204705. https://doi.org/10.1063/1.5024862

Journal Article Type Article
Acceptance Date May 10, 2018
Online Publication Date May 29, 2018
Publication Date May 29, 2018
Deposit Date May 14, 2018
Publicly Available Date Mar 29, 2024
Journal Journal of Chemical Physics
Print ISSN 0021-9606
Electronic ISSN 1089-7690
Publisher American Institute of Physics
Peer Reviewed Peer Reviewed
Volume 148
Issue 20
Article Number 204705
DOI https://doi.org/10.1063/1.5024862
Public URL https://nottingham-repository.worktribe.com/output/931603
Publisher URL https://aip.scitation.org/doi/10.1063/1.5024862

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