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

DOI: 10.1039/D3NR04690G

Authors: Benedikt P. Klein (Diamond Light Source; University of Warwick) , Matthew A. Stoodley (Diamond Light Source; University of Warwick) , Dylan B. Morgan (University of Warwick) , Luke A. Rochford (Diamond Light Source) , Leon B. S. Williams (Diamond Light Source) , Paul T. P. Ryan (Diamond Light Source; Imperial College London) , Lars Sattler (Carl von Ossietzky Universität Oldenburg) , Sebastian M. Weber (Carl von Ossietzky Universität Oldenburg) , Gerhard Hilt (Carl von Ossietzky Universität Oldenburg) , Thomas J. Liddy (Diamond Light Source; University of Nottingham) , Tien-Lin Lee (Diamond Light Source) , Reinhard Maurer (University of Warwick; University of Glasgow) , David A. Duncan (Diamond Light Source)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Nanoscale

State: Published (Approved)
Published: February 2024
Diamond Proposal Number(s): 27138 , 25379 , 33709

Abstract: 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.

Subject Areas: Chemistry, Physics


Instruments: I09-Surface and Interface Structural Analysis

Added On: 28/02/2024 14:35

Documents:
d3nr04690g.pdf

Discipline Tags:

Surfaces Physics Physical Chemistry Chemistry

Technical Tags:

Diffraction Spectroscopy X-ray Standing Wave (XSW) X-ray Photoelectron Spectroscopy (XPS)