Relativistic calculations on the adsorption of CO on the (111) surfaces of Ni, Pd, and Pt within the zeroth-order regular approximation

In this paper we first describe the implementation of the zeroth-order regular approximation (ZORA) for relativistic effects in our density-functional program for extended systems. The ZORA formalism affords approximations, which are discussed and tested, that reduce the computational effort of scalar relativistic calculations to that of nonrelativistic calculations, the inclusion of spin-orbit coupling requiring additional effort. Second, we present the outcome of nonrelativistic, scalar relativistic, and spin-orbit coupling calculations on the adsorption energy of CO on the (111) surfaces of Ni, Pd, and Pt. Relativity has a modest effect for CO on Pd, but proves to be essential for CO on Pt. The relativistic correction for the CO/Pt adsorption energy is as large as 70% at the scalar relativistic level and 55% when including spin-orbit coupling. In addition, relativity changes the preferred adsorption site for CO/Pt from hollow to top. We have examined the effects of spin polarization and of different exchange-correlation functionals, i.e., the local-density approximation (LDA) versus two generalized gradient approximations (GGA). The GGA’s correct the severe overbinding by LDA of CO to the metal surfaces, and yield good agreement with experiment for adsorption energies and sites.