Polarization-induced renormalization of molecular levels at metallic and semiconducting surfaces

TL;DR

This study uses first-principles G0W0 calculations to analyze how substrate polarization affects molecular energy levels at surfaces, revealing a scaling relationship with substrate electronic properties and explaining the limitations of common DFT functionals.

Contribution

It provides a microscopic understanding of polarization-induced level shifts at surfaces and relates these shifts to the substrate's electronic structure using GW calculations and simple models.

Findings

Level gap reduction scales with substrate density of states or band gap.

GW calculations match well with experimental trends for level shifts.

Semi-local functionals have errors canceled, giving good occupied orbital energies.

Abstract

On the basis of first-principles G0W0 calculations we study systematically how the electronic levels of a benzene molecule are renormalized by substrate polarization when physisorbed on different metallic and semiconducting surfaces. The polarization-induced reduction of the energy gap between occupied and unoccupied molecular levels is found to scale with the substrate density of states at the Fermi level (for metals) and substrate band gap (for semiconductors). These conclusions are further supported by GW calculations on simple lattice models. By expressing the electron self-energy in terms of the substrate's joint density of states we relate the level shift to the surface electronic structure thus providing a microscopic explanation of the trends in the G0W0 calculations. While image charge effects are not captured by semi-local and hybrid exchange-correlation functionals, we find that error cancellations lead to remarkably good agreement between the G0W0 and Kohn-Sham energies for the occupied orbitals of the adsorbed molecule.