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Updated: Aug 22, 2025
In Situ SIMS and IR Spectroscopy of Well-defined Surfaces Prepared by Soft Landing of Mass-selected Ions
Published on: June 16, 2014
Active Spaces and Non-Orthogonal Configuration Interaction Approaches for Investigating Molecules on Metal Surfaces
Junhan Chen1, Wenjie Dou2,3, Joseph Subotnik1
1Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104, United States.
Abstract:
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.
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