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Exploring ultra-fast charge transfer and vibronic coupling with N 1s RIXS maps of an aromatic molecule coupled to a semiconductor

O'Shea, James N.; Handrup, Karsten LU ; Temperton, Robert H.; Gibson, Andrew J.; Nicolaou, Alessandro and Jaouen, Nicolas (2017) In Journal of Chemical Physics 147(13).
Abstract

We present for the first time two-dimensional resonant inelastic x-ray scattering (RIXS) maps of multilayer and monolayer bi-isonicotinic acid adsorbed on the rutile TiO2(110) single crystal surface. This enables the elastic channel to be followed over the lowest unoccupied molecular orbitals resonantly excited at the N 1s absorption edge. The data also reveal ultra-fast intramolecular vibronic coupling, particularly during excitation into the lowest unoccupied molecular orbital-derived resonance. Both elastic scattering and the vibronic coupling loss features are expected to contain the channel in which the originally excited electron is directly involved in the core-hole decay process. This allows RIXS data for a molecule... (More)

We present for the first time two-dimensional resonant inelastic x-ray scattering (RIXS) maps of multilayer and monolayer bi-isonicotinic acid adsorbed on the rutile TiO2(110) single crystal surface. This enables the elastic channel to be followed over the lowest unoccupied molecular orbitals resonantly excited at the N 1s absorption edge. The data also reveal ultra-fast intramolecular vibronic coupling, particularly during excitation into the lowest unoccupied molecular orbital-derived resonance. Both elastic scattering and the vibronic coupling loss features are expected to contain the channel in which the originally excited electron is directly involved in the core-hole decay process. This allows RIXS data for a molecule coupled to a wide bandgap semiconductor to be considered in the same way as the core-hole clock implementation of resonant photoemission spectroscopy (RPES). However, contrary to RPES measurements, we find no evidence for the depletion of the participator channel under the conditions of ultra-fast charge transfer from the molecule to the substrate densities of states, on the time scale of the core-hole lifetime. These results suggest that the radiative core-hole decay processes in RIXS are not significantly modified by charge transfer on the femtosecond time scale in this system.

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organization
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Contribution to journal
publication status
published
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in
Journal of Chemical Physics
volume
147
issue
13
publisher
American Institute of Physics
external identifiers
  • scopus:85030999966
ISSN
0021-9606
DOI
10.1063/1.4999135
language
English
LU publication?
yes
id
78732fe4-7cfb-4905-9119-51699ffa640a
date added to LUP
2017-10-26 14:35:45
date last changed
2018-10-03 09:28:09
@article{78732fe4-7cfb-4905-9119-51699ffa640a,
  abstract     = {<p>We present for the first time two-dimensional resonant inelastic x-ray scattering (RIXS) maps of multilayer and monolayer bi-isonicotinic acid adsorbed on the rutile TiO<sub>2</sub>(110) single crystal surface. This enables the elastic channel to be followed over the lowest unoccupied molecular orbitals resonantly excited at the N 1s absorption edge. The data also reveal ultra-fast intramolecular vibronic coupling, particularly during excitation into the lowest unoccupied molecular orbital-derived resonance. Both elastic scattering and the vibronic coupling loss features are expected to contain the channel in which the originally excited electron is directly involved in the core-hole decay process. This allows RIXS data for a molecule coupled to a wide bandgap semiconductor to be considered in the same way as the core-hole clock implementation of resonant photoemission spectroscopy (RPES). However, contrary to RPES measurements, we find no evidence for the depletion of the participator channel under the conditions of ultra-fast charge transfer from the molecule to the substrate densities of states, on the time scale of the core-hole lifetime. These results suggest that the radiative core-hole decay processes in RIXS are not significantly modified by charge transfer on the femtosecond time scale in this system.</p>},
  articleno    = {134705},
  author       = {O'Shea, James N. and Handrup, Karsten and Temperton, Robert H. and Gibson, Andrew J. and Nicolaou, Alessandro and Jaouen, Nicolas},
  issn         = {0021-9606},
  language     = {eng},
  month        = {10},
  number       = {13},
  publisher    = {American Institute of Physics},
  series       = {Journal of Chemical Physics},
  title        = {Exploring ultra-fast charge transfer and vibronic coupling with N 1s RIXS maps of an aromatic molecule coupled to a semiconductor},
  url          = {http://dx.doi.org/10.1063/1.4999135},
  volume       = {147},
  year         = {2017},
}