title: Unexpected interplay of bonding height and energy level alignment at heteromolecular hybrid interfaces.
abstract: Although geometric and electronic properties of any physical or chemical system are always mutually coupled by the rules of quantum mechanics, counterintuitive coincidences between the two are sometimes observed. The coadsorption of the organic molecules 3,4,9,10-perylene tetracarboxylic dianhydride and copper-II-phthalocyanine on Ag(111) represents such a case, since geometric and electronic structures appear to be decoupled: one molecule moves away from the substrate while its electronic structure indicates a stronger chemical interaction, and vice versa for the other. Our comprehensive experimental and ab-initio theoretical study reveals that, mediated by the metal surface, both species mutually amplify their charge-donating and -accepting characters, respectively. This resolves the apparent paradox, and demonstrates with exceptional clarity how geometric and electronic bonding parameters are intertwined at metal-organic interfaces.
authors.affiliation: 1] Peter Grünberg Institut (PGI-3), Forschungszentrum Jülich, 52425 Jülich, Germany [2] Jülich Aachen Research Alliance (JARA)-Fundamentals of Future Information Technology, 52425 Jülich, Germany [3].
authors.forename: Benjamin
authors.initials: B
authors.lastname: Stadtmüller
authors.affiliation: Institut für Physik, Karl-Franzens-Universität Graz, Graz 8010, Austria.
authors.forename: Daniel
authors.initials: D
authors.lastname: Lüftner
authors.affiliation: 1] Peter Grünberg Institut (PGI-3), Forschungszentrum Jülich, 52425 Jülich, Germany [2] Jülich Aachen Research Alliance (JARA)-Fundamentals of Future Information Technology, 52425 Jülich, Germany.
authors.forename: Martin
authors.initials: M
authors.lastname: Willenbockel
authors.affiliation: Institut für Physik, Karl-Franzens-Universität Graz, Graz 8010, Austria.
authors.forename: Eva M
authors.initials: EM
authors.lastname: Reinisch
authors.affiliation: 1] Peter Grünberg Institut (PGI-3), Forschungszentrum Jülich, 52425 Jülich, Germany [2] Jülich Aachen Research Alliance (JARA)-Fundamentals of Future Information Technology, 52425 Jülich, Germany.
authors.forename: Tomoki
authors.initials: T
authors.lastname: Sueyoshi
authors.affiliation: Institut für Physik, Karl-Franzens-Universität Graz, Graz 8010, Austria.
authors.forename: Georg
authors.initials: G
authors.lastname: Koller
authors.affiliation: 1] Peter Grünberg Institut (PGI-3), Forschungszentrum Jülich, 52425 Jülich, Germany [2] Jülich Aachen Research Alliance (JARA)-Fundamentals of Future Information Technology, 52425 Jülich, Germany.
authors.forename: Serguei
authors.initials: S
authors.lastname: Soubatch
authors.affiliation: Institut für Physik, Karl-Franzens-Universität Graz, Graz 8010, Austria.
authors.forename: Michael G
authors.initials: MG
authors.lastname: Ramsey
authors.affiliation: Institut für Physik, Karl-Franzens-Universität Graz, Graz 8010, Austria.
authors.forename: Peter
authors.initials: P
authors.lastname: Puschnig
authors.affiliation: 1] Peter Grünberg Institut (PGI-3), Forschungszentrum Jülich, 52425 Jülich, Germany [2] Jülich Aachen Research Alliance (JARA)-Fundamentals of Future Information Technology, 52425 Jülich, Germany.
authors.forename: F Stefan
authors.initials: FS
authors.lastname: Tautz
authors.affiliation: 1] Peter Grünberg Institut (PGI-3), Forschungszentrum Jülich, 52425 Jülich, Germany [2] Jülich Aachen Research Alliance (JARA)-Fundamentals of Future Information Technology, 52425 Jülich, Germany.
authors.forename: Christian
authors.initials: C
authors.lastname: Kumpf
mesh_terms: D000327:Adsorption; D000812:Anhydrides / Q000737:chemistry*; D003300:Copper / Q000737:chemistry*; D008956:Models, Chemical; D009942:Organometallic Compounds / Q000737:chemistry*; D010569:Perylene / Q000031:analogs & derivatives* / Q000737:chemistry; D011789:Quantum Theory; D012834:Silver / Q000737:chemistry*
chemical_list: C521594:3,4,9,10-perylenetetracarboxylic dianhydride; D000812:Anhydrides; D009942:Organometallic Compounds; D012834:Silver; D010569:Perylene; D003300:Copper