Planar and cagelike structures of gold clusters: Density-functional pseudopotential calculations

TL;DR

This study uses density functional theory to explore why gold forms planar and cage-like clusters, revealing the importance of relativistic effects and electronic shell filling in their stability.

Contribution

It demonstrates that scalar-relativistic pseudopotentials and GGA are essential for accurately predicting gold cluster geometries, highlighting the role of relativistic effects in gold's unique structures.

Findings

Planar Au_n structures are lower in energy with scalar-relativistic pseudopotentials and GGA.

Cage-like structures of Au clusters are meta-stable at high temperatures.

Gold clusters exhibit strong screening due to d-electrons, affecting their polarizability.

Abstract

We study why gold forms planar and cage-like clusters while copper and silver do not. We use density functional theory and norm-conserving pseudo-potentials with and without a scalar relativistic component. For the exchange-correlation functional we use both the generalized gradient (GGA) and the local density (LDA) approximations. We find that planar Au_n structures, with up to n = 11, have lower energy than the three-dimensional isomers only with scalar-relativistic pseudopotentials and the GGA. In all other calculations, with more than 6 or 7 noble metal atoms, we obtain three dimensional structures. In the total energy balance, kinetic energy favors planar and cage structures, while xc-energy favors 3D structures. As a second step, we construct cluster structures having only surface atoms with Oh, Td, and Ih symmetry. Then we select those with 2(l+1)**2 electrons (with l integer), which correspond to the filling of a spherical electronic shell formed by node-less one electron wave functions. Using scalar relativistic GGA molecular dynamics at T = 600K, we show that the cage-like structures of neutral Au32, Au50, and Au162 are meta-stable. The dipole polarizability of gold clusters corresponds to the linear response of 1.6 delocalized valence electrons, suggesting a strong screening of the valence interactions due to the d-electrons.