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Abstract

In interfaces between inorganic and biological materials relevant for technological applications, the general challenge of structure determination is exacerbated by the high flexibility of bioorganic components, chemical bonding, and charge rearrangement at the interface. In this paper, we investigate a chemically complex building block, namely, the arginine (Arg) amino acid interfaced with Cu, Ag, and Au (111) surfaces. We investigate how the environment changes the accessible conformational space of this amino acid by building and analyzing a database of thousands of structures optimized with the Perdew‐Burke‐Ernzerhof (PBE) functional, including screened pairwise van der Waals interactions. When in contact with metallic surfaces, the accessible space for Arg is dramatically reduced, while the one for Arg‐H⁺ is instead increased if compared to the gas phase. This is explained by the formation of strong bonds between Arg and the surfaces and by their absence and charge screening on Arg‐H⁺ upon adsorption. We also observe protonation‐dependent stereoselective binding of the amino acid to the metal surfaces: Arg adsorbs with its chiral C_α H center pointing H away from the surfaces, while Arg‐H⁺ adsorbs with H pointing toward the surface.