Long-Range Surface-Assisted Molecule-Molecule Hybridization.
density functional theory
intermolecular interactions
metal-organic complexes
non-contact atomic force microscopy
scanning tunneling microscopy and spectroscopy
surface chemistry
Journal
Small (Weinheim an der Bergstrasse, Germany)
ISSN: 1613-6829
Titre abrégé: Small
Pays: Germany
ID NLM: 101235338
Informations de publication
Date de publication:
Mar 2021
Mar 2021
Historique:
received:
24
09
2020
revised:
15
12
2020
pubmed:
13
2
2021
medline:
13
2
2021
entrez:
12
2
2021
Statut:
ppublish
Résumé
Metalated phthalocyanines (Pc's) are robust and versatile molecular complexes, whose properties can be tuned by changing their functional groups and central metal atom. The electronic structure of magnesium Pc (MgPc)-structurally and electronically similar to chlorophyll-adsorbed on the Ag(100) surface is investigated by low-temperature scanning tunneling microscopy and spectroscopy, non-contact atomic force microscopy, and density functional theory. Single, isolated MgPc's exhibit a flat, fourfold rotationally symmetric morphology, with doubly degenerate, partially populated (due to surface-to-molecule electron transfer) lowest unoccupied molecular orbitals (LUMOs). In contrast, MgPc's with neighbouring molecules in proximity undergo a lift of LUMOs degeneracy, with a near-Fermi local density of states with reduced twofold rotational symmetry, indicative of a long-range attractive intermolecular interaction. The latter is assigned to a surface-mediated two-step electronic hybridization process. First, LUMOs interact with Ag(100) conduction electrons, forming hybrid molecule-surface orbitals with enhanced spatial extension. Then, these delocalized molecule-surface states further hybridize with those of neighbouring molecules. This work highlights how the electronic structure of molecular adsorbates-including orbital degeneracies and symmetries-can be significantly altered via surface-mediated intermolecular hybridization, over extended distances (beyond 3 nm), having important implications for prospects of molecule-based solid-state technologies.
Identifiants
pubmed: 33576182
doi: 10.1002/smll.202005974
doi:
Types de publication
Journal Article
Langues
eng
Sous-ensembles de citation
IM
Pagination
e2005974Subventions
Organisme : Australian Research Council
ID : FT150100426
Organisme : Monash Centre of Atomically Thin Materials
Informations de copyright
© 2021 Wiley-VCH GmbH.
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