Cysteine adsorption on the Au(111) surface and the electron transfer in configuration of a scanning tunneling microscope: A quantum-chemical approach

Adsorption of two forms, molecule and radical, of amino acid L-cysteine (Cys) on the Au₁₂ cluster that simulates the (111) face of single-crystal gold is studied in the framework of the density functional theory. Effects of solvation of adsorbed Cys particles and lateral interaction in a monolayer are analyzed. The simulation predicts a commensurate adsorption energetics of the molecule and radical, with a difference between the “on-top,” “hollow,” and “bridge” positions. An analysis of lateral electrostatic interactions points to the stability of a cluster comprising six Cys particles, which conforms to the size of a fragment observed experimentally. Adsorption calculations are used to build three-dimensional isosurfaces (STM images), where the tungsten needle of the scanning tunneling microscope is simulated by a tungsten atom or by small clusters. The calculated images are sensitive to both the Cys shape and the orientation of adsorbed Cys particles. Calculation results are compared with fresh in situ submolecular-resolution STM data. Simulated images (with commensurate contributions made by sulfur atom and amino group) built for Cys radical adsorbed in the “on-top” position give best conformance to experiment.