Evaluation of basis sets with 11-electron analytic effective core potentials of gold for modeling molecular...

Three types of 11-electron analytic effective core potentials (ECPs) and their corresponding double-zeta and single-zeta basis sets of gold are evaluated using density functional theory (DFT) calculations. We find that, compared with basis sets derived for use with Hatree-Fock-based Los Alamos (LANL1) and Ermler-Christiansen (EC) ECPs, the DFT-derived Troullier-Martins (TM) ECP together with a single-zeta basis set (TMSZ) is more suitable to describe not only the interaction between gold atoms with a benzene-1,4-dithiolate molecule but also the electronic structure of an infinite 1-dimensional monatomic gold chain. Hence, TMSZ is the best single-zeta basis set with an 11-electron ECP for gold available currently to be used in theoretical calculations on electrical properties of molecular electronic devices with DFT based Green's function method employing a finite analytic basis of local orbitals.