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

TL;DR

This study uses first-principles simulations to analyze how thermal and electronic fluctuations influence the adsorption behavior of azobenzene molecules on Ag(111), highlighting the importance of entropy and electronic correlations.

Contribution

It introduces a comprehensive first-principles approach combining molecular dynamics and many-body dispersion to accurately model finite-temperature adsorption of flexible molecules.

Findings

Adsorption is strongly entropy-driven with high desorption prefactors.

Finite-temperature effects dominate the behavior of flexible molecules on surfaces.

First-principles methods effectively reveal collective fluctuations in complex adsorbate systems.

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.