Combined orbital tomography study of multi-configurational molecular adsorbate systems

Pavel Kliuiev, Giovanni Zamborlini, Matteo Jugovac, Yeliz Gurdal, Karin von Arx, Kay Waltar, Stephan Schnidrig, Roger Alberto, Marcella Iannuzzi, Vitaliy Feyer, Matthias Hengsberger, Jürg Osterwalder, Luca Castiglioni*

*Corresponding author for this work

Research output: Contribution to journalArticleScientificpeer-review

9 Citations (Scopus)
28 Downloads (Pure)


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 3 d 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.

Original languageEnglish
Article number5255
Number of pages6
JournalNature Communications
Issue number1
Publication statusPublished - 1 Dec 2019
MoE publication typeA1 Journal article-refereed


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