Abstract
Using a combination of ab initio and semiempirical methods, adsorption problems on surfaces with large unit cells and low symmetry can still be studied. Here, a hybrid approach of density functional theory (DFT) and Hartree–Fock (HF) was used. As an example, we determined the geometry and the electronic properties of benzoic acid (BA), salicylic acid (SA) and para‐salicylic acid (p‐SA) adsorbed on MgSO~4~⋅H~2~O (100), which are used as conditioner molecules for the electrostatic separation of minerals. Contrary to general expectations, these molecules are chemisorbed, with binding energies around 1.9 eV, forming bonds through the carboxylic O atom of the COOH groups in a nonplanar geometry, although the surface is a stoichiometric wide‐band‐gap insulator and the molecules stay intact. In contrast, a planar adsorption geometry turned out to be nonbonding. Bonding takes place by means of surface–molecule resonances due to the overlap of the valence band with molecular orbitals, assisted by a small charge‐transfer molecule to the surface of around 0.15__e__. These combined interactions cause an intramolecular twist between the COOH group and the benzene ring.