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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 LU ; Temperton, Robert H.; Gibson, Andrew J.; Nicolaou, Alessandro; Jaouen, Nicolas; Taylor, John B.; Mayor, Louise C.; Swarbrick, Janine C. and Schnadt, Joachim LU (2018) In Journal of Chemical Physics 148(20).
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... (More)

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.

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author
organization
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type
Contribution to journal
publication status
published
subject
in
Journal of Chemical Physics
volume
148
issue
20
publisher
American Institute of Physics
external identifiers
  • scopus:85047857528
ISSN
0021-9606
DOI
10.1063/1.5024862
language
English
LU publication?
yes
id
b3f0d86f-7b4b-483c-bf0a-23df8fad766a
date added to LUP
2018-06-13 12:59:53
date last changed
2018-10-03 09:28:23
@article{b3f0d86f-7b4b-483c-bf0a-23df8fad766a,
  abstract     = {<p>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 TiO<sub>2</sub>(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.</p>},
  articleno    = {204705},
  author       = {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},
  issn         = {0021-9606},
  language     = {eng},
  month        = {05},
  number       = {20},
  publisher    = {American Institute of Physics},
  series       = {Journal of Chemical Physics},
  title        = {Ultra-fast intramolecular vibronic coupling revealed by RIXS and RPES maps of an aromatic adsorbate on TiO<sub>2</sub>(110)},
  url          = {http://dx.doi.org/10.1063/1.5024862},
  volume       = {148},
  year         = {2018},
}