Adsorption of prototypical amino acids on silica: Influence of the pre-adsorbed water multilayer

We explore the interaction between acetic acid, some typical α-amino acids (α-AAs), and a fully hydroxylated (0001) surface of α-quartz by means of theoretical calculations based on the density functional theory (DFT) under periodic boundary conditions. The influence of microsolvation, represented by a water multilayer, and dispersion forces is analyzed. All the considered molecules strongly adsorb on the hydroxylated surface and prefer to adsorb molecularly. The inclusion of dispersion forces increases the interaction energies by 15–30 kJ/mol, without significant changes in structure and mode of adsorption except for histidine where the interaction is improved through protonation of the α-amine group. When the water multilayer is included a decrease in the surface–adsorbate interaction energies is observed. Also, some α-AAs, glycine and alanine, change their adsorption mode and, now, the more stable structure is the zwitterion. Adsorption as zwitterions is always favored with respect to molecular interaction when dispersion forces are taken into account. Comparing the energies of adsorbed and solvated α-AA zwitterions, it turns out that inclusion of dispersion forces predicts that solvated zwitterions are the lower energy configurations.