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Combined orbital tomography study of multi-configurational molecular adsorbate systems


Kliuiev, Pavel; Zamborlini, Giovanni; Jugovac, Matteo; Gurdal, Yeliz; Arx, Karin von; Waltar, Kay; Schnidrig, Stephan; Alberto, Roger; Iannuzzi, Marcella; Feyer, Vitaliy; Hengsberger, Matthias; Osterwalder, Jürg; Castiglioni, Luca (2019). Combined orbital tomography study of multi-configurational molecular adsorbate systems. Nature Communications, 10(1):5255.

Abstract

Molecular reactivity is determined by the energy levels and spatial extent of the frontier orbitals. Orbital tomography based on angle-resolved photoelectron spectroscopy is an elegant method to study the electronic structure of organic adsorbates, however, it is conventionally restricted to systems with one single rotational domain. In this work, we extend orbital tomography to systems with multiple rotational domains. We characterise the hydrogen evolution catalyst Co-pyrphyrin on an Ag(110) substrate and compare it with the empty pyrphyrin ligand. In combination with low-energy electron diffraction and DFT simulations, we fully determine adsorption geometry and both energetics and spatial distributions of the valence electronic states. We find two states close to the Fermi level in Co-pyrphyrin with Co 3d character that are not present in the empty ligand. In addition, we identify several energetically nearly equivalent adsorption geometries that are important for the understanding of the electronic structure. The ability to disentangle and fully elucidate multi-configurational systems renders orbital tomography much more useful to study realistic catalytic systems.

Abstract

Molecular reactivity is determined by the energy levels and spatial extent of the frontier orbitals. Orbital tomography based on angle-resolved photoelectron spectroscopy is an elegant method to study the electronic structure of organic adsorbates, however, it is conventionally restricted to systems with one single rotational domain. In this work, we extend orbital tomography to systems with multiple rotational domains. We characterise the hydrogen evolution catalyst Co-pyrphyrin on an Ag(110) substrate and compare it with the empty pyrphyrin ligand. In combination with low-energy electron diffraction and DFT simulations, we fully determine adsorption geometry and both energetics and spatial distributions of the valence electronic states. We find two states close to the Fermi level in Co-pyrphyrin with Co 3d character that are not present in the empty ligand. In addition, we identify several energetically nearly equivalent adsorption geometries that are important for the understanding of the electronic structure. The ability to disentangle and fully elucidate multi-configurational systems renders orbital tomography much more useful to study realistic catalytic systems.

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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
07 Faculty of Science > Physics Institute
08 Research Priority Programs > Solar Light to Chemical Energy Conversion
Dewey Decimal Classification:530 Physics
Uncontrolled Keywords:General Biochemistry, Genetics and Molecular Biology, General Physics and Astronomy, General Chemistry
Language:English
Date:1 December 2019
Deposited On:18 Dec 2019 16:14
Last Modified:05 Feb 2020 16:05
Publisher:Nature Publishing Group
ISSN:2041-1723
OA Status:Gold
Free access at:Publisher DOI. An embargo period may apply.
Publisher DOI:https://doi.org/10.1038/s41467-019-13254-7
Project Information:
  • : FunderSNSF
  • : Grant IDCRSII2_160801
  • : Project TitlePhotocatalytic Processes at Solvated Interfaces

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