Theoretical modelling of the adsorption of thallium and element 113 atoms on gold using two-component density functional methods with effective core potentials

Abstract

The adsorption of thallium and element 113 atoms on a gold surface has been modelled by cluster calculations. Quasirelativistic two-component density functional calculations that include spin–orbit coupling self-consistently have been used together with spin-dependent effective core potentials. The validity of this method is demonstrated by comparisons with high-level wave function based calculations on the hetero-dimers AuTl and Au(113). New basis sets had to be generated because standard basis sets optimized for scalar-relativistic calculations are too inflexible to describe the different behaviour of the atomic sub-shells that result from the spin–orbit interaction. The topmost layer of gold atoms within the cluster was allowed to fully relax upon adsorption, and different adsorption sites (on-top, hollow, and bridge) on the (100) and (111) surfaces were considered. Spin–orbit coupling reduces the surface binding energies of an element 113 atom much more than it does for Tl, such that the binding energy of element 113 to the gold cluster, as compared to Tl, is reduced by 90±15kJ/mol in most cases. Together with the experimental result for thallium, this allows an estimate of the adsorption temperature of element 113 in thermochromatography experiments.