Publications
Chlorination of zirconium (0001) surface: A first-principles study
The mechanisms and energetics of Zr(0001) surface chlorination by dissociative adsorption of gaseous Cl2, and associated speciation and surface degradation processes, have been investigated within the framework of density functional theory. Chlorination of Zr(0001) is predicted to be exothermic by 3 eV/Cl for dissociative adsorption of a single Cl2 molecule, followed by exothermic chlorination to 1ML and 2 ML under Cl-rich conditions, with respective energy gains of 1.93 and 2.79 eV/Cl. Calculations also show that exfoliation of the top Cl-Zr-Cl sandwich layers is exothermic and most energetically favorable, and can thus be considered as a leading mechanism for Zr(0001) surface dissolution. Finally, consistent with experimental findings, formation of ZrCl4 molecular products is also found to be dominant during Zr(0001) chlorination.