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Combined orbital tomography study of multi-configurational molecular adsorbate systems

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...

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Autores principales: 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
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group UK 2019
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6868194/
https://www.ncbi.nlm.nih.gov/pubmed/31748503
http://dx.doi.org/10.1038/s41467-019-13254-7
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author 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
author_facet 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
author_sort Kliuiev, Pavel
collection PubMed
description 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 [Formula: see text] 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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spelling pubmed-68681942019-11-22 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 Nat Commun Article 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 [Formula: see text] 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. Nature Publishing Group UK 2019-11-20 /pmc/articles/PMC6868194/ /pubmed/31748503 http://dx.doi.org/10.1038/s41467-019-13254-7 Text en © The Author(s) 2019 Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/.
spellingShingle Article
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
Combined orbital tomography study of multi-configurational molecular adsorbate systems
title Combined orbital tomography study of multi-configurational molecular adsorbate systems
title_full Combined orbital tomography study of multi-configurational molecular adsorbate systems
title_fullStr Combined orbital tomography study of multi-configurational molecular adsorbate systems
title_full_unstemmed Combined orbital tomography study of multi-configurational molecular adsorbate systems
title_short Combined orbital tomography study of multi-configurational molecular adsorbate systems
title_sort combined orbital tomography study of multi-configurational molecular adsorbate systems
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6868194/
https://www.ncbi.nlm.nih.gov/pubmed/31748503
http://dx.doi.org/10.1038/s41467-019-13254-7
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