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

O'Shea, James N. and Handrup, Karsten and Temperton, Robert H. and Gibson, Andrew J. and Nicolaou, Alessandro and Jaouen, Nicolas and Taylor, John B. and Mayor, Louise C. and Swarbrick, Janine C. and Schnadt, Joachim (2018) Ultra-fast intramolecular vibronic coupling revealed by RIXS and RPES maps of an aromatic adsorbate on TiO2(110). Journal of Chemical Physics . ISSN 1089-7690 (In Press)

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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.

Item Type: Article
Schools/Departments: University of Nottingham, UK > Faculty of Science > School of Physics and Astronomy
Depositing User: Eprints, Support
Date Deposited: 14 May 2018 08:36
Last Modified: 14 May 2018 16:19
URI: http://eprints.nottingham.ac.uk/id/eprint/51756

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