Corrosion inhibition at emergent grain boundaries studied by DFT for 2-mercaptobenzothiazole on bi-crystalline copper.

Inhibition of the initiation of intergranular corrosion was modeled at the atomic scale for 2-mercaptobenzothiazole (MBT) adsorbed on a (110)-oriented copper bi-crystal exposing an emergent Σ9 coincident site lattice (CSL) grain boundary (GB) using dispersion-corrected density functional theory (DFT-D). At both isolated molecule and full, dense monolayer coverages, the molecule adsorbed on the grain and GB sites stands perpendicular or tilted with no parallel orientation to the surface being favored. Chemical bonding of the thione and thiolate conformers involves both S atoms or the exocyclic S and N atoms, respectively. The full, dense monolayer is formed with a net gain in energy per surface area, but at the cost of a significant molecule deformation. It significantly enhances the Cu vacancy formation energy at the grain and GB sites, revealing that MBT also inhibits Cu dissolution for the more susceptible GBs with efficiency depending on atomic density of GB emergence. [ABSTRACT FROM AUTHOR]