Probing the role of surface termination in the adsorption of azupyrene on copper.

Autor: Klein BP; Diamond Light Source, Harwell Science and Innovation Campus, Didcot, OX11 0DE, UK. david.duncan@diamond.ac.uk.; Department of Chemistry, University of Warwick, Gibbet Hill Road, Coventry, CV4 7AL, UK. r.maurer@warwick.ac.uk., Stoodley MA; Diamond Light Source, Harwell Science and Innovation Campus, Didcot, OX11 0DE, UK. david.duncan@diamond.ac.uk.; Department of Chemistry, University of Warwick, Gibbet Hill Road, Coventry, CV4 7AL, UK. r.maurer@warwick.ac.uk., Morgan DB; Department of Chemistry, University of Warwick, Gibbet Hill Road, Coventry, CV4 7AL, UK. r.maurer@warwick.ac.uk., Rochford LA; Diamond Light Source, Harwell Science and Innovation Campus, Didcot, OX11 0DE, UK. david.duncan@diamond.ac.uk., Williams LBS; Diamond Light Source, Harwell Science and Innovation Campus, Didcot, OX11 0DE, UK. david.duncan@diamond.ac.uk.; School of Chemistry, University of Glasgow, University Avenue, Glasgow, G12 8QQ, UK.; School of Physics and Astronomy, University of Glasgow, University Avenue, Glasgow, G12 8QQ, UK., Ryan PTP; Diamond Light Source, Harwell Science and Innovation Campus, Didcot, OX11 0DE, UK. david.duncan@diamond.ac.uk.; Department of Materials, Imperial College London, Prince Consort Rd, SW7 2AZ, UK., Sattler L; Institut für Chemie, Carl von Ossietzky Universität Oldenburg, Carl-von-Ossietzky-Straße 9-11, 26111 Oldenburg, Germany., Weber SM; Institut für Chemie, Carl von Ossietzky Universität Oldenburg, Carl-von-Ossietzky-Straße 9-11, 26111 Oldenburg, Germany., Hilt G; Institut für Chemie, Carl von Ossietzky Universität Oldenburg, Carl-von-Ossietzky-Straße 9-11, 26111 Oldenburg, Germany., Liddy TJ; Diamond Light Source, Harwell Science and Innovation Campus, Didcot, OX11 0DE, UK. david.duncan@diamond.ac.uk.; School of Chemistry, University of Nottingham, University Park, Nottingham, NG7 2RD, UK., Lee TL; Diamond Light Source, Harwell Science and Innovation Campus, Didcot, OX11 0DE, UK. david.duncan@diamond.ac.uk., Maurer RJ; Department of Chemistry, University of Warwick, Gibbet Hill Road, Coventry, CV4 7AL, UK. r.maurer@warwick.ac.uk.; Department of Physics, University of Warwick, Gibbet Hill Road, Coventry, CV4 7AL, UK., Duncan DA; Diamond Light Source, Harwell Science and Innovation Campus, Didcot, OX11 0DE, UK. david.duncan@diamond.ac.uk.
Jazyk: angličtina
Zdroj: Nanoscale [Nanoscale] 2024 Mar 14; Vol. 16 (11), pp. 5802-5812. Date of Electronic Publication: 2024 Mar 14.
DOI: 10.1039/d3nr04690g
Abstrakt: The role of the inorganic substrate termination, within the organic-inorganic interface, has been well studied for systems that contain strong localised bonding. However, how varying the substrate termination affects coordination to delocalised electronic states, like that found in aromatic molecules, is an open question. Azupyrene, a non-alternant polycyclic aromatic hydrocarbon, is known to bind strongly to metal surfaces through its delocalised π orbitals, thus yielding an ideal probe into delocalised surface-adsorbate interactions. Normal incidence X-ray standing wave (NIXSW) measurements and density functional theory calculations are reported for the adsorption of azupyrene on the (111), (110) and (100) surface facets of copper to investigate the dependence of the adsorption structure on the substrate termination. Structural models based on hybrid density functional theory calculations with non-local many-body dispersion yield excellent agreement with the experimental NIXSW results. No statistically significant difference in the azupyrene adsorption height was observed between the (111) and (100) surfaces. On the Cu(110) surface, the molecule was found to adsorb 0.06 ± 0.04 Å closer to the substrate than on the other surface facets. The most energetically favoured adsorption site on each surface, as determined by DFT, is subtly different, but in each case involved a configuration where the aromatic rings were centred above a hollow site, consistent with previous reports for the adsorption of small aromatic molecules on metal surfaces.
Databáze: MEDLINE
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