Controlling the Adsorption of Aromatic Compounds on Pt(111) with Oxygenate Substituents: From DFT to Simple Molecular Descriptors

Aromatic
chemistry on metallic surfaces is involved in many processes
within the contexts of biomass valorization, pollutant degradation,
or corrosion protection. Albeit theoretically and experimentally challenging,
knowing the structure and the stability of aromatic compounds on such
surfaces is essential to understand their properties. To gain insights
on this topic, we performed periodic ab initio calculations on Pt(111)
to determine a set of simple molecular descriptors that predict both
the stability and the structure of aromatic adsorbates substituted
with alkyl and alkoxy (or hydroxy) groups. While the van der Waals
(vdW) interaction is controlled by the molecular weight and the deformation
energy by both the nature and the relative position of the substituents
to the surface, the chemical bonding can be correlated to the Hard
and Soft Acids and Bases (HSAB) interaction energy. This work gives
general insights on the interaction of aromatic compounds with the
Pt(111) surface.