First-principles Newns-Anderson Hamiltonian Construction for Chemisorbed Hydrogen at Metal Surfaces

TL;DR

This paper introduces a first-principles method to construct Newns-Anderson Hamiltonians for chemisorbed hydrogen on metal surfaces, enabling more accurate modeling of adsorption phenomena beyond traditional approximations.

Contribution

It presents a novel approach using projection operator diabatisation with DFT data to build Hamiltonians for gas-solid interfaces, validated on hydrogen-metal systems.

Findings

Good agreement with reference calculations for electronic and vibrational lifetimes

Wideband limit approximation valid for H/Al(111) but limited for H/Cu(111) and H/Pt(111)

Method enables more accurate first-principles modeling of chemisorption phenomena

Abstract

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 diabatisation 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 tunnelling lifetimes, and vibrational lifetimes from the constructed Newns-Anderson Hamiltonians and find good agreement with reference calculations. 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).