First-principles Newns–Anderson Hamiltonian construction for chemisorbed hydrogen at metal surfaces

The Newns–Anderson Hamiltonian is widely used to describe adsorption at gas–solid interfaces, yet its construction typically relies on simplifying assumptions, such as constant coupling and the wideband limit approximation. Here, we present a first-principles approach to construct Newns–Anderson Hamiltonians by applying projection operator diabatization to Hamiltonian matrices obtained from Kohn–Sham density functional theory calculations. We demonstrate this method for chemisorbed hydrogen on three fcc metal(111) surfaces: Al, Cu, and Pt. To validate the electronic coupling between adsorbed hydrogen and the metal surface, we compute the projected density of states, electronic tunneling lifetimes, and vibrational lifetimes from the constructed Newns–Anderson Hamiltonians and find good agreement with reference calculations. The analysis of the chemisorption function reveals that the wideband limit approximation is valid for H/Al(111) but has limited applicability for H/Cu(111) and H/Pt(111).