Density Distribution in the Liquid Hg-Sapphire Interface

TL;DR

This study uses advanced quantum Monte Carlo simulations to accurately model the density distribution at the liquid mercury-sapphire interface, aligning well with experimental data without assuming charge transfer.

Contribution

It extends the self-consistent quantum Monte Carlo method to the liquid metal-solid interface, providing new insights into interfacial structure without charge transfer assumptions.

Findings

Simulation results agree with experimental density profiles.

Van der Waals interactions explain interfacial structure.

Charge transfer is not necessary to model the interface.

Abstract

We present the results of a computer simulation study of the liquid density distribution normal to the interface between liquid Hg and the reconstructed (0001) face of sapphire. The simulations are based on an extension of the self-consistent quantum Monte Carlo scheme previously used to study the structure of the liquid metal-vapor interface. The calculated density distribution is in very good agreement with that inferred from the recent experimental data of Tamam et al (J. Phys. Chem. Lett. 1, 1041-1045 (2010)). We conclude that, to account for the difference in structure between the liquid Hg-vapor and liquid-Hg-reconstructed (0001) Al2O3 interfaces, it is not necessary assume there is charge transfer from the Hg to the Al2O3. Rather, the available experimental data are adequately reproduced when the van der Waals interactions of the Al and O atoms with Hg atoms and the exclusion of electron density from Al2O3 via repulsion of the electrons from the closed shells of the ions in the solid are accounted for.