Dibenzyl disulfide adsorption on Cu(111) surface: a DFT study

Abstract

The adsorption of dibenzyl disulfide (DBDS) on a Cu(111) surface model was investigated by using density functional (DFT) calculations, considering energetic and electronic aspects. Several complexes were generated, where the bridge, hollow hcp, hollow fcc and top adsorption sites were considered. The results show that the Cu-S interaction guides the final complexes, and a secondary π-Cu weak interaction confers an extra stability. The complexes were grouped as physi-or chemi-sorption according to their adsorption energy applying a distortion decomposition model, with a preference by a double interaction of S with Cu (i.e. hollow hcp, and bridge sites). A degree of disulfide bond dissociation was observed in the complexes, being correlated with adsorption energies. From an electronic aspect, it was found that the electronic flow from copper to DBDS occurs in the most stables complexes, checked with charge analysis.These results are agreed with experimental revelations of copper corrosion on power transformers.

1,2,3-Benzotriazole derivatives adsorption on Cu(1 1 1) surface: A DFT study

“…Small organic molecules adsorbed on metal surfaces are studied in order to understand the more fundamental chemical phenomena occurring at the surface/molecule interface. 31 In the present paper, the nature of the interaction between copper surface, Cu(111), and some BTAH derivatives are theoretically studied and compared with the results obtained in experimental assays of copper corrosion/inhibition in dielectric oils, in line with our former studies [32][33][34] . Our results are compared with those previously reported for similar systems as well as with similar works, clarifying some unclear aspects related to copper passivation.…”

“…as also used previously in our studies 32,33 , consists of energetic contributions of deformation (E def ) and interaction (E int ), related as:…”

“…The present study considers a new perspective on the inhibition of copper corrosion process produced by DBDS. In earlier studies, the adsorption of DBDS over a Cu(111) surface was characterized, and disulfide bond dissociation was observed in the complexes obtained by the chemisorption mechanism 32,33 . It was linked to the charge transfer processes in which higher deformation energy of the adsorbate was observed.…”