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arXiv · 1603.03363

Thermal and electronic fluctuations of flexible adsorbed molecules: Azobenzene on Ag(111)

Reinhard J. Maurer·Wei Liu·Igor Poltavsky·Thomas Stecher·Harald Oberhofer·Karsten Reuter·Alexandre Tkatchenko
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Abstract

We investigate the thermal and electronic collective fluctuations that contribute to the finite-temperature adsorption properties of flexible adsorbates on surfaces on the example of the molecular switch azobenzene C$_{12}$H$_{10}$N$_{2}$ on the Ag(111) surface. Using first-principles molecular dynamics simulations we obtain the free energy of adsorption that accurately accounts for entropic contributions, whereas the inclusion of many-body dispersion interactions accounts for the electronic correlations that govern the adsorbate binding. We find the adsorbate properties to be strongly entropy-driven, as can be judged by a kinetic molecular desorption prefactor of 10$^{24}$ s$^{-1}$ that largely exceeds previously reported estimates. We relate this effect to sizable fluctuations across structural and electronic observables. Comparison of our calculations to temperature-programmed desorption measurements demonstrates that finite-temperature effects play a dominant role for flexible molecules in contact with polarizable surfaces, and that recently developed first-principles methods offer an optimal tool to reveal novel collective behavior in such complex systems.

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Reinhard J. Maurer, Wei Liu, Igor Poltavsky, Thomas Stecher, Harald Oberhofer, Karsten Reuter, Alexandre Tkatchenko. 2016-03-10. Thermal and electronic fluctuations of flexible adsorbed molecules: Azobenzene on Ag(111). https://doi.org/10.1103/physrevlett.116.146101

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