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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...
Autores principales: | , , , , , , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Nature Publishing Group UK
2019
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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. |
format | Online Article Text |
id | pubmed-6868194 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2019 |
publisher | Nature Publishing Group UK |
record_format | MEDLINE/PubMed |
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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