Active Spaces and Non-Orthogonal Configuration Interaction Approaches for Investigating Molecules on Metal Surfaces

We test a set of multiconfigurational wavefunction approaches for calculating the ground state electron population for a two-site Anderson model representing a molecule on a metal surface. In particular, we compare (i) a Hartree Fock like wavefunction where frontier orbitals are allowed to be nonorthogonal versus (ii) a fully non-orthogonal configuration interaction wavefunction based on constrained Hartree-Fock states. We test both the strong and weak metal-molecule hybridization (Γ) limits as well as the strong and weak electron-electron repulsion (U) limits. We obtain accurate results as compared with exact numerical renormalization group theory, recovering charge transfer states where appropriate. The current framework should open a path to run molecular non-adiabatic dynamics on metal surfaces.