Repository: Freie Universität Berlin, Math Department

Kinetic Trapping of Charge-Transfer Molecules at Metal Interfaces

Werkovits, A. and Hollweger, S. and Niederreiter, M. and Risse, T. and Cartus, J.J. and Sterrer, M. and Matera, S. (2024) Kinetic Trapping of Charge-Transfer Molecules at Metal Interfaces. The Journal of Physical Chemistry C .

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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.

Item Type:Article
Subjects:Mathematical and Computer Sciences > Mathematics > Applied Mathematics
Divisions:Department of Mathematics and Computer Science > Institute of Mathematics > Geophysical Fluid Dynamics Group
ID Code:3116
Deposited By: Ulrike Eickers
Deposited On:21 Feb 2024 11:27
Last Modified:21 Feb 2024 11:27

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