A global optimisation study of the low-lying isomers of the alumina octomer (Al$_2$O$_3$)$_8$

TL;DR

This study combines Monte-Carlo Basin-Hopping and density functional theory to identify low-energy alumina octomer structures, revealing a new global minimum and a stability limit around 1300-1450 K.

Contribution

It introduces a combined computational approach to accurately determine the global minimum structures of alumina clusters, including a novel candidate shape.

Findings

Discovered a new global minimum candidate for alumina octomers.

Identified a stability limit for alumina clusters at 1300-1450 K.

Revealed elongated shapes of low-energy alumina clusters.

Abstract

We employ the Monte-Carlo Basin-Hopping (MC-BH) global optimisation technique with inter- atomic pair potentials to generate low-energy candidates of stoichiometric alumina octomers ((Al$_2$O$_3$)$_8$). The candidate structures are subsequently refined with density functional theory calculations employing hybrid functionals (B3LYP and PBE0) and a large basis set (6-311+G(d)) including a vibrational analysis. We report the discovery of a set of energetically low-lying alumina octomer clusters, including a new global minimum candidate, with shapes that are elongated rather than spherical. We find a stability limit for these and smaller-sized clusters at a temperature of $T\simeq1300-1450$ K corresponding to a phase transition in liquid alumina.