Large-scale surface reconstruction energetics of Pt(100) and Au(100) by all-electron DFT

TL;DR

This study uses all-electron DFT to accurately compare the reconstruction energies of Au(100) and Pt(100) surfaces, resolving discrepancies between experiments and previous theories by emphasizing large supercell models.

Contribution

The paper demonstrates that large supercell models are essential in DFT calculations to correctly capture the reconstruction energetics of Au(100) and Pt(100) surfaces, aligning theory with experimental data.

Findings

Large supercells are necessary for accurate reconstruction energy predictions.

Reconstruction energies for Au(100) and Pt(100) are similar when properly modeled.

Electronic reconstruction is identified as the driving force behind surface reconstruction.

Abstract

The low-index surfaces of Au and Pt all tend to reconstruct, a fact that is of key importance in many nanostructure, catalytic, and electrochemical applications. Remarkably, some significant questions regarding their structural energies remain even today, in particular for the large-scale quasihexagonal reconstructed (100) surfaces: Rather dissimilar reconstruction energies for Au and Pt in available experiments, and experiment and theory do not match for Pt. We here show by all-electron density-functional theory that only large enough "(5 x N)" approximant supercells capture the qualitative reconstruction energy trend between Au(100) and Pt(100), in contrast to what is often done in the theoretical literature. Their magnitudes are then in fact similar, and closer to the measured value for Pt(100); our calculations achieve excellent agreement with known geometric characteristics and provide direct evidence for the electronic reconstruction driving force.