# Gallium Trichloride Fluid: Dimer Dissociation Mechanism, Local Structure, and Atomic Dynamics

## TL;DR

This paper studies the structure and behavior of gallium trichloride fluid to improve metal recycling processes.

## Contribution

The study reveals the dimer dissociation mechanism and atomic dynamics in supercritical gallium trichloride using first-principles simulations.

## Key findings

- Dimer dissociation involves intermediate corner-sharing CS-Ga2Cl6 structures.
- GaCl3 monomers partially disproportionate at high temperatures and low pressures.
- Supercritical gallium trichloride exhibits unusual atomic dynamics.

## Abstract

Molten gallium trichloride emerges as a promising solvent for oxidative metal recycling. The use of supercritical fluid enhances the performance and kinetics of metal dissolution due to significantly lower viscosity in the reaction media. Additionally, the dual molecular nature of gallium trichloride, existing as edge-sharing ES-Ga2Cl6 dimers at low temperatures and high pressure, or flat trigonal GaCl3 monomers in the vicinity of the critical point and low pressures, creates the possibility to tailor the chemical geometry to a particular metallic species. Nevertheless, the mechanism of dimer dissociation, local structure, and atomic dynamics in supercritical gallium trichloride fluids are not known. Using first-principles molecular dynamics, validated by comparison with our high-energy X-ray diffraction results, we illustrate the elementary steps in dimer dissociation. These include the formation of intermediate corner-sharing CS-Ga2Cl6 dimers, the partial disproportionation of GaCl3 monomers at high temperatures and low pressures, changes in the local environment of molecular entities, and unusual atomic dynamics in supercritical fluids.