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

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.

6 pages, 3 figures, accepted for publication in Phys. Rev. Lett

References in corpus (2)

• Perspective: Advances and challenges in treating van der Waals dispersion forces in density functional theory
• van der Waals forces in density functional theory: The vdW-DF method

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• Global Structure Search for Molecules on Surfaces: Efficient Sampling with Curvilinear Coordinates
• Computational design of metal-supported molecular switches: Transient ion formation during light- and electron-induced isomerisation of azobenzene