Local Space Approximation Methods for Correlated Electronic Structure Calculations in Large Delocalized Systems that are Locally Perturbed

Abstract

Rigorous electronic structure calculations including correlation at all common levels of theory are feasible for large delocalized systems that are locally perturbed using the generic local space approximation (LSA). The basic ideas involved in the LSA are reviewed in the context of a single determinant Hartree-Fock or Kohn-Sham treatment. It is, then, shown how this treatment can be extended so as to explicitly incorporate local many-body interactions. For a problem such as a catalytic reaction on a metal surface the translational symmetry of the bare metal can be readily exploited. Several ‘proof of the method’ studies are discussed which demonstrate that accuracy improves monotonically as the size of the local region is increased and that the initial rate of convergence is rapid.