Density functional theory beyond the generalized gradient approximation for surface chemistry

Abstract

Density functional theory with generalized gradient approximations (GGAs) for the exchange-correlation density functional is widely used to model adsorption and reaction of molecules on surfaces. In other areas of computational chemistry, GGAs have largely been replaced by more accurate meta-GGA and hybrid approximations. Meta-GGAs and hybrids can ameliorate GGAs’ systematic over-delocalization of electrons and systematic underestimate of reaction barriers. This chapter discusses extensions of meta-GGAs and screened hybrids to surface chemistry. It reviews evidence that GGAs’ systematic underestimate of gas-phase reaction barriers carries over to reactions on surfaces, and that meta-GGAs and screened hybrids can improve results. It closes with recent applications and new work towards more accurate functionals for surfaces. These promising results motivate further exploration of meta-GGAs and screened hybrids for surface chemistry.