Kinetic Trapping of Charge-Transfer Molecules at Metal Interfaces.

Autor:	Werkovits A; Institute of Solid State Physics, Graz University of Technology, Petersgasse 16/II, 8010 Graz, Austria., Hollweger SB; Institute of Solid State Physics, Graz University of Technology, Petersgasse 16/II, 8010 Graz, Austria., Niederreiter M; Institute of Physics, University of Graz, Universitätsplatz 5, 8010 Graz, Austria., Risse T; Institut für Chemie und Biochemie, Freie Universität Berlin, Arminallee 22, 14195 Berlin, Germany., Cartus JJ; Institute of Solid State Physics, Graz University of Technology, Petersgasse 16/II, 8010 Graz, Austria., Sterrer M; Institute of Physics, University of Graz, Universitätsplatz 5, 8010 Graz, Austria., Matera S; Theory Department, Fritz Haber Institute of the MPG, Faradayweg 4-6, 14195 Berlin-Dahlem, Germany., Hofmann OT; Institute of Solid State Physics, Graz University of Technology, Petersgasse 16/II, 8010 Graz, Austria.
Jazyk:	angličtina
Zdroj:	The journal of physical chemistry. C, Nanomaterials and interfaces [J Phys Chem C Nanomater Interfaces] 2024 Feb 07; Vol. 128 (7), pp. 3082-3089. Date of Electronic Publication: 2024 Feb 07 (Print Publication: 2024).
DOI:	10.1021/acs.jpcc.3c08262
Abstrakt:	Despite the common expectation that conjugated organic molecules on metals adsorb in a flat-lying layer, several recent studies have found coverage-dependent transitions to upright-standing phases, which exhibit notably different physical properties. In this work, we argue that from an energetic perspective, thermodynamically stable upright-standing phases may be more common than hitherto thought. However, for kinetic reasons, this phase may often not be observed experimentally. Using first-principles kinetic Monte Carlo simulations, we find that the structure with lower molecular density is (almost) always formed first, reminiscent of Ostwald's rule of stages. The phase transitions to the upright-standing phase are likely to be kinetically hindered under the conditions typically used in surface science. The simulation results are experimentally confirmed for the adsorption of tetracyanoethylene on Cu(111) using infrared and X-ray photoemission spectroscopy. Investigating both the role of the growth conditions and the energetics of the interface, we find that the time for the phase transition is determined mostly by the deposition rate and, thus, is mostly independent of the nature of the molecule. Competing Interests: The authors declare no competing financial interest. (© 2024 The Authors. Published by American Chemical Society.)
Databáze:	MEDLINE
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