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@ARTICLE{Haags:1046002,
author = {Haags, Anja and Reichmann, Alexander and Ruan, Zilin and
Fan, Qitang and Egger, Larissa and Kirschner, Hans and
Naumann, Tim and Werner, Simon and Kleykamp, Olaf and
Martinez-Castro, Jose and Lüpke, Felix and Bocquet,
François C. and Kumpf, Christian and Soubatch, Serguei and
Gottwald, Alexander and Koller, Georg and Ramsey, Michael G.
and Richter, Mathias and Sundermeyer, Jörg and Puschnig,
Peter and Gottfried, J. Michael and Tautz, F. Stefan and
Wenzel, Sabine},
title = {{M}ulti-{O}rbital {C}harge {T}ransfer into {N}onplanar
{C}ycloarenes {R}evealed with {CO}-{F}unctionalized {T}ips},
publisher = {arXiv},
reportid = {FZJ-2025-03649},
year = {2025},
abstract = {On-surface synthesis has allowed for the tuneable
preparation of numerous molecular systems with variable
properties. Recently, we demonstrated the highly selective
synthesis of kekulene $(>99\%)$ on Cu(111) and isokekulene
$(92\%)$ on Cu(110) from the same molecular precursor (Ruan
et al., Angew. Chem. Int. Ed. 2025, e202509932). Scanning
tunneling microscopy with CO-functionalized tips can
identify the single molecules on the basis of their
geometric structure at a low coverage on Cu(110), but it
also detects complex features due to electronic
contributions close to the Fermi energy. Here, we
investigate the origin of these features by simulating STM
images based on a weighted sum of multiple molecular
orbitals, for which we employ weights based on the
calculated molecular-orbital projected density of states.
This allows for an experimental confirmation of charge
transfer from the surface into multiple formerly unoccupied
molecular orbitals for single molecules of kekulene as well
as isokekulene in its two nonplanar adsorption
configurations. In comparison, the area-integrating
photoemission orbital tomography technique confirms the
charge transfer as well as the high selectivity for the
formation of a full monolayer of mainly isokekulene on
Cu(110). Our STM-based approach is applicable to a wide
range of adsorbed molecular systems and specifically also
suited for strongly interacting surfaces, nonplanar
molecules, and such molecules which can only be prepared at
extremely low yields.},
keywords = {Chemical Physics (physics.chem-ph) (Other) / Materials
Science (cond-mat.mtrl-sci) (Other) / FOS: Physical sciences
(Other)},
cin = {PGI-3},
cid = {I:(DE-Juel1)PGI-3-20110106},
pnm = {5213 - Quantum Nanoscience (POF4-521) / SFB 1083 A12 -
Struktur und Anregungen von hetero-epitaktischen
Schichtsystemen aus schwach wechselwirkenden 2D-Materialien
und molekularen Schichten (A12) (385975694) / TACY -
Tackling the Cyclacene Challenge (101071420) / DFG project
G:(GEPRIS)511561801 - Manipulierung von 2D Supraleitung und
Majorana Zuständen auf der Nanoskala (511561801) / ML4Q -
Machine Learning for Quantum (101120240)},
pid = {G:(DE-HGF)POF4-5213 / G:(GEPRIS)385975694 /
G:(EU-Grant)101071420 / G:(GEPRIS)511561801 /
G:(EU-Grant)101120240},
typ = {PUB:(DE-HGF)25},
doi = {10.48550/ARXIV.2509.00736},
url = {https://juser.fz-juelich.de/record/1046002},
}