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@ARTICLE{Klein:861478,
author = {Klein, Benedikt P. and van der Heijden, Nadine J. and
Kachel, Stefan R. and Franke, Markus and Krug, Claudio K.
and Greulich, Katharina K. and Ruppenthal, Lukas and
Müller, Philipp and Rosenow, Phil and Parhizkarmazinani,
Shayan and Posseik, Francois and Schmid, Martin and
Hieringer, Wolfgang and Maurer, Reinhard J. and Tonner, Ralf
and Kumpf, Christian and Swart, Ingmar and Gottfried, J.
Michael},
title = {{M}olecular {T}opology and the {S}urface {C}hemical {B}ond:
{A}lternant {V}ersus {N}onalternant {A}romatic {S}ystems as
{F}unctional {S}tructural {E}lements},
journal = {Physical review / X Expanding access X},
volume = {9},
number = {1},
issn = {2160-3308},
address = {College Park, Md.},
publisher = {APS},
reportid = {FZJ-2019-01943},
pages = {011030},
year = {2019},
abstract = {The interaction of carbon-based aromatic molecules and
nanostructures with metals can strongly depend on the
topology of their π-electron systems. This is shown with a
model system using the isomers azulene, which has a
nonalternant π system with a 5-7 ring structure, and
naphthalene, which has an alternant π system with a 6-6
ring structure. We found that azulene can interact much more
strongly with metal surfaces. On copper (111), its
zero-coverage desorption energy is 1.86 eV, compared to 1.07
eV for naphthalene. The different bond strengths are
reflected in the adsorption heights, which are 2.30 Å for
azulene and 3.04 Å for naphthalene, as measured by the
normal incidence x-ray standing wave technique. These
differences in the surface chemical bond are related to the
electronic structure of the molecular π systems. Azulene
has a low-lying LUMO that is close to the Fermi energy of Cu
and strongly hybridizes with electronic states of the
surface, as is shown by photoemission, near-edge x-ray
absorption fine-structure, and scanning tunneling microscopy
data in combination with theoretical analysis. According to
density functional theory calculations, electron donation
from the surface into the molecular LUMO leads to negative
charging and deformation of the adsorbed azulene. Noncontact
atomic force microscopy confirms the deformation, while
Kelvin probe force microscopy maps show that adsorbed
azulene partially retains its in-plane dipole. In contrast,
naphthalene experiences only minor adsorption-induced
changes of its electronic and geometric structure. Our
results indicate that the electronic properties of
metal-organic interfaces, as they occur in organic
(opto)electronic devices, can be tuned through modifications
of the π topology of the molecular organic semiconductor,
especially by introducing 5-7 ring pairs as functional
structural elements.},
cin = {PGI-3},
ddc = {530},
cid = {I:(DE-Juel1)PGI-3-20110106},
pnm = {143 - Controlling Configuration-Based Phenomena (POF3-143)
/ DFG project 396769409 - Grundlagen der
Photoemissionstomographie},
pid = {G:(DE-HGF)POF3-143 / G:(GEPRIS)396769409},
typ = {PUB:(DE-HGF)16},
UT = {WOS:000458822800001},
doi = {10.1103/PhysRevX.9.011030},
url = {https://juser.fz-juelich.de/record/861478},
}