title: Energy Ordering of Molecular Orbitals.
abstract: Orbitals are invaluable in providing a model of bonding in molecules or between molecules and surfaces. Most present-day methods in computational chemistry begin by calculating the molecular orbitals of the system. To what extent have these mathematical objects analogues in the real world? To shed light on this intriguing question, we employ a photoemission tomography study on monolayers of 3,4,9,10-perylene-tetracarboxylic acid dianhydride (PTCDA) grown on three Ag surfaces. The characteristic photoelectron angular distribution enables us to assign individual molecular orbitals to the emission features. When comparing the resulting energy positions to density functional calculations, we observe deviations in the energy ordering. By performing complete active space calculations (CASSCF), we can explain the experimentally observed orbital ordering, suggesting the importance of static electron correlation beyond a (semi)local approximation. On the other hand, our results also show reality and robustness of the orbital concept, thereby making molecular orbitals accessible to experimental observations.
authors.affiliation: Institute of Physics, University of Graz, NAWI-Graz, Universitätsplatz 5, 8010 Graz, Austria.
authors.forename: P
authors.identifier: http://orcid.org/0000-0002-8057-7795
authors.initials: P
authors.lastname: Puschnig
authors.affiliation: Institute of Chemistry, University of Graz, NAWI Graz, Heinrichstraße 28/IV, 8010 Graz, Austria.
authors.forename: A D
authors.identifier: http://orcid.org/0000-0001-7388-778X
authors.initials: AD
authors.lastname: Boese
authors.affiliation: Peter Grünberg Institut (PGI-3), Forschungszentrum Jülich , 52425 Jülich, Germany.|Jülich Aachen Research Alliance (JARA), Fundamentals of Future Information Technology, 52425 Jülich, Germany.
authors.forename: M
authors.initials: M
authors.lastname: Willenbockel
authors.affiliation: Peter Grünberg Institut (PGI-3), Forschungszentrum Jülich , 52425 Jülich, Germany.|Jülich Aachen Research Alliance (JARA), Fundamentals of Future Information Technology, 52425 Jülich, Germany.
authors.forename: M
authors.initials: M
authors.lastname: Meyer
authors.affiliation: Institute of Physics, University of Graz, NAWI-Graz, Universitätsplatz 5, 8010 Graz, Austria.
authors.forename: D
authors.initials: D
authors.lastname: Lüftner
authors.affiliation: Institute of Physics, University of Graz, NAWI-Graz, Universitätsplatz 5, 8010 Graz, Austria.
authors.forename: E M
authors.initials: EM
authors.lastname: Reinisch
authors.affiliation: Institute of Physics, University of Graz, NAWI-Graz, Universitätsplatz 5, 8010 Graz, Austria.
authors.forename: T
authors.initials: T
authors.lastname: Ules
authors.affiliation: Institute of Physics, University of Graz, NAWI-Graz, Universitätsplatz 5, 8010 Graz, Austria.
authors.forename: G
authors.initials: G
authors.lastname: Koller
authors.affiliation: Peter Grünberg Institut (PGI-3), Forschungszentrum Jülich , 52425 Jülich, Germany.|Jülich Aachen Research Alliance (JARA), Fundamentals of Future Information Technology, 52425 Jülich, Germany.
authors.forename: S
authors.initials: S
authors.lastname: Soubatch
authors.affiliation: Institute of Physics, University of Graz, NAWI-Graz, Universitätsplatz 5, 8010 Graz, Austria.
authors.forename: M G
authors.initials: MG
authors.lastname: Ramsey
authors.affiliation: Peter Grünberg Institut (PGI-3), Forschungszentrum Jülich , 52425 Jülich, Germany.|Jülich Aachen Research Alliance (JARA), Fundamentals of Future Information Technology, 52425 Jülich, Germany.
authors.forename: F S
authors.initials: FS
authors.lastname: Tautz