Structure of Molten FeCl2 and FeCl3

TL;DR

This study elucidates the atomic-scale structures of molten FeCl2 and FeCl3 using advanced experimental and computational methods, revealing key differences and providing benchmarks for future modeling of molten salts.

Contribution

It combines HEXRD, EPSR, and machine learning MD simulations to accurately determine and compare the structures of molten FeCl2 and FeCl3, establishing reliable models and structural benchmarks.

Findings

Both melts mainly consist of extended chains with six or more Fe centers.

The study confirms the octahedral to tetrahedral transition of Fe upon melting.

Diffusion coefficients for the melts were calculated and compared.

Abstract

Molten iron chlorides are central to emerging energy technologies, including electrochemical iron production and redox flow batteries. Optimizing their electrochemical performance and transport properties requires atomic-scale structural understanding, yet detailed data for molten FeCl2 and its differences from FeCl3 remain scarce. Here, we determined the structures of molten FeCl2 and FeCl3 using High Energy X-ray diffraction (HEXRD), Empirical Potential Structure Refinement (EPSR), and molecular dynamics (MD) simulations with machine learning interatomic potentials (MLIPs). HEXRD measurements provided structure factors and total radial distribution functions (RDFs), which were quantitatively reproduced through EPSR refinement directly constrained by experimental data. MD simulations using MACE foundation and fine-tuned models reproduced experimental structure factors as well as total and partial RDFs, capturing key structural differences between the melts. The models resolved the octahedral to tetrahedral coordination transition of Fe upon melting in FeCl3 and predicted a similar transition in FeCl2. Analysis of MD trajectories quantified coordination environments, bridging Cl populations, bond-angle distributions, and connectivity patterns, revealing distinct degrees of polymerization and local geometry. Polymer chain statistics further showed that, contrary to prior reports, both liquids predominantly consist of extended chains containing six or more Fe centers rather than discrete Fe2Cl6 units. Finally, diffusion coefficients of the two melts calculated from the MACE-MD simulations were compared. Together, these results establish atomic-scale structural benchmarks for molten FeCl2 and FeCl3 and demonstrate the reliability of MACE-based MLIPs for predictive modeling of high-temperature molten salts, while providing practical guidance for MLIP development in complex ionic liquids.