Ab initio free energies of liquid metal alloys: Application to the phase diagrams of Li-Na and K-Na

Huang, Yang; Widom, Michael; Gao, Michael C.

doi:10.1103/physrevmaterials.6.013802

Title: Ab initio free energies of liquid metal alloys: Application to the phase diagrams of Li-Na and K-Na

Journal Article · 10 January 2022 · Physical Review Materials

DOI: https://doi.org/10.1103/physrevmaterials.6.013802 · OSTI ID:1843617

Huang, Yang ^[1];

^[1];

^[2]

Carnegie Mellon Univ., Pittsburgh, PA (United States)
National Energy Technology Lab. (NETL), Albany, OR (United States)

Comparison of free energies between different phases and different compositions underlies the prediction of alloy phase diagrams. To allow direct comparison, consistent reference points for the energies or enthalpies are required, and the entropy must be placed on an absolute scale, yielding absolute free energies. Here we derive absolute free energies of liquids from ab-initio molecular dynamics (AIMD) by combining the directly simulated enthalpies with an entropy derived from simulated densities and pair correlation functions. Additionally, as an example of the power of this method we calculate the phase diagrams of two binary alkali metal alloys, Li-Na and K-Na, revealing a critical point and liquid-liquid phase separation in the former case, and a deep eutectic in the latter. Good agreement with experimental data demonstrates the power of this simple method.

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Research Organization:: National Energy Technology Laboratory (NETL), Pittsburgh, PA, Morgantown, WV, and Albany, OR (United States)

Sponsoring Organization:: USDOE Office of Fossil Energy (FE)

Grant/Contract Number:: SC0014506

OSTI ID:: 1843617

Journal Information:: Physical Review Materials, Journal Name: Physical Review Materials Journal Issue: 1 Vol. 6; ISSN 2475-9953

Publisher:: American Physical Society (APS)Copyright Statement

Country of Publication:: United States

Language:: English

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Title: Ab initio free energies of liquid metal alloys: Application to the phase diagrams of Li-Na and K-Na

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