Electric-field-driven direct desulfurization

Bogdana Borca, Tomasz Michnowicz, Remi Petuya, Marcel Pristl, Verena Schendel, Ivan Pentegov, Ulrike Kraft, Hagen Klauk, Peter Wahl, Rico Gutzler, Andres Arnau, Uta Schlickum, Klaus Kern

Research output: Contribution to journalArticlepeer-review

23 Citations (Scopus)


The 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.
Original languageEnglish
Pages (from-to)4703–4709
JournalACS Nano
Issue number5
Early online date24 Apr 2017
Publication statusPublished - 23 May 2017


  • STM
  • DFT
  • Tetracenothiophene
  • Desulfurization
  • Electric field
  • Single molecules


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