From Bulk to Surface: Structure and Dynamics of Amorphous Alumina from Deep Potential Molecular Dynamics

TL;DR

This study uses Deep Potential molecular dynamics to model amorphous alumina surfaces at the atomic level, revealing detailed structural and dynamic properties that are difficult to measure experimentally.

Contribution

It introduces a machine learning-based approach to generate large-scale, ab initio-quality models of amorphous alumina surfaces, improving understanding of their structure and dynamics.

Findings

The DP model accurately reproduces experimental glass structure.

Surface density recovers to bulk values within ~10 Å.

Surface hosts under-coordinated motifs like AlO3 and OAl2.

Abstract

Understanding the atomic-scale structure and dynamics of amorphous oxide surfaces is essential for interpreting their chemical reactivity, mechanical stability, and interfacial behavior, yet direct experimental characterization remains challenging. We employ Deep Potential (DP) molecular dynamics to generate large-scale, ab initio-quality models of amorphous Al$_2$O$_3$ bulk glasses and melt-quenched free surfaces, enabling a quantitative analysis of both structure and relaxation dynamics with statistical confidence inaccessible to direct ab initio simulation. The trained DP model reproduces experimental liquid and glass structure, captures the cooling-rate dependence of the bulk glass transition, and corrects systematic biases in the polyhedral populations predicted by widely used classical force fields. At the free surface, mass density recovers to bulk values over ~10 $\unicode{x212B}$, while local coordination requires a slightly wider subsurface region to fully converge. The outermost layer is oxygen-enriched, exhibits altered polyhedral connectivity with contracted Al-O bonds, and hosts a broad population of under-coordinated motifs (notably AlO$_3$ and OAl$_2$) whose abundances are governed by glass stability. These reactive Lewis acid and Br$\unicode{x00F8}$nsted base sites are locally paired in a manner consistent with bond-valence compensation, yet remain spatially dispersed rather than aggregating into extended clusters. Despite this pronounced structural heterogeneity, the surface relaxes on the same timescale as the bulk and exhibits a comparable glass transition temperature, suggesting that the disordered surface is kinetically stable once formed. Together, these results establish a molecular-level picture of amorphous alumina surfaces and demonstrate the capability of machine-learned potentials to resolve structure-property relationships in disordered oxide interfaces.