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dc.contributor.authorBorca, Bogdana
dc.contributor.authorMichnowicz, Tomasz
dc.contributor.authorPetuya, Remi
dc.contributor.authorPristl, Marcel
dc.contributor.authorSchendel, Verena
dc.contributor.authorPentegov, Ivan
dc.contributor.authorKraft, Ulrike
dc.contributor.authorKlauk, Hagen
dc.contributor.authorWahl, Peter
dc.contributor.authorGutzler, Rico
dc.contributor.authorArnau, Andres
dc.contributor.authorSchlickum, Uta
dc.contributor.authorKern, Klaus
dc.identifier.citationBorca , B , Michnowicz , T , Petuya , R , Pristl , M , Schendel , V , Pentegov , I , Kraft , U , Klauk , H , Wahl , P , Gutzler , R , Arnau , A , Schlickum , U & Kern , K 2017 , ' Electric-field-driven direct desulfurization ' , ACS Nano , vol. 11 , no. 5 , pp. 4703–4709 .
dc.identifier.otherPURE: 250199738
dc.identifier.otherPURE UUID: a5b4affc-9fd2-465b-9f2c-52e7800ba378
dc.identifier.otherScopus: 85019887779
dc.identifier.otherORCID: /0000-0002-8635-1519/work/46939674
dc.identifier.otherWOS: 000402498400035
dc.description.abstractThe ability to elucidate the elementary steps of a chemical reaction at the atomic scale is important for the detailed understanding of the processes involved, which is key to uncover avenues for improved reaction paths. Here, we track the chemical pathway of an irreversible direct desulfurization reaction of tetracenothiophene adsorbed on the Cu(111) closed-packed surface at the submolecular level. Using the precise control of the tip position in a scanning tunneling microscope and the electric field applied across the tunnel junction, the two carbon–sulfur bonds of a thiophene unit are successively cleaved. Comparison of spatially mapped molecular states close to the Fermi level of the metallic substrate acquired at each reaction step with density functional theory calculations reveals the two elementary steps of this reaction mechanism. The first reaction step is activated by an electric field larger than 2 V nm–1, practically in absence of tunneling electrons, opening the thiophene ring and leading to a transient intermediate. Subsequently, at the same threshold electric field and with simultaneous injection of electrons into the molecule, the exergonic detachment of the sulfur atom is triggered. Thus, a stable molecule with a bifurcated end is obtained, which is covalently bound to the metallic surface. The sulfur atom is expelled from the vicinity of the molecule.
dc.relation.ispartofACS Nanoen
dc.rights© 2017, American Chemical Society. This work has been made available online in accordance with the publisher’s policies. This is the author created, accepted version manuscript following peer review and may differ slightly from the final published version. The final published version of this work is available at /
dc.subjectElectric fielden
dc.subjectSingle moleculesen
dc.subjectQC Physicsen
dc.subjectQD Chemistryen
dc.subjectTK Electrical engineering. Electronics Nuclear engineeringen
dc.titleElectric-field-driven direct desulfurizationen
dc.typeJournal articleen
dc.contributor.institutionUniversity of St Andrews. School of Physics and Astronomyen
dc.contributor.institutionUniversity of St Andrews. Condensed Matter Physicsen
dc.description.statusPeer revieweden

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