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Thermodynamic origin of entropy-assisted stabilization in multicomponent rock-salt oxides

  • Supriya Ghosal
  • Swapan Pati
  • Ashutosh Kumar
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Abstract

High entropy oxides are commonly associated with high configurational entropy (ΔSconf≥ 1.61R) corresponding to five equimolar cations occupying a crystallographic sublattice. However, recent experimental observations indicate that medium-entropy compositions may also exhibit entropy-stabilized rock-salt phases, raising an important question regarding the minimum entropy required for phase stabilization. In this work, we employ a first-principles thermodynamic framework to investigate the stability of rock-salt oxides containing two to five principal cations components analogous to (Ni0.8Cu0.2)O, (Ni0.6Cu0.2Zn0.2)O, (Ni0.4Cu0.2Zn0.2Co0.2)O, (Ni0.2Cu0.2Zn0.2Co0.2Mg0.2)O. Density functional theory, MCSQS-based structural modeling, and finite-temperature Gibbs free-energy analysis are combined to quantify the roles of enthalpy mixing (ΔHmix), configurational (ΔSconf), vibrational (ΔSvib), electronic and magnetic (ΔSmag) contributions towards (ΔSelec) entropy change in governing phase stability. The results show that ΔSconf alone is not a universal descriptor of phase stability. While the two-cation system is enthalpy-stabilized but three-, four- and five-cation systems become thermodynamically stable at high-temperature due to entropy-driven reduction of the Gibbs free energy. These findings demonstrate that single-phase rock-salt oxides are not restricted to the conventional high-entropy limit and that medium-entropy compositions can also be stabilized under suitable thermodynamic conditions.

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Cite

BibTeXRIS
BibTeX
@misc{ghosal2026thermodynamic,
  title = {{Thermodynamic origin of entropy-assisted stabilization in multicomponent rock-salt oxides}},
  author = {Supriya Ghosal and Swapan Pati and Ashutosh Kumar},
  howpublished = {arXiv},
  year = {2026},
  month = oct,
  doi = {10.48550/arxiv.2606.00753},
  eprint = {2606.00753},
  archivePrefix = {arXiv},
  url = {https://arxiv.org/abs/2606.00753},
}
RIS
TY  - UNPB
TI  - Thermodynamic origin of entropy-assisted stabilization in multicomponent rock-salt oxides
AU  - Supriya Ghosal
AU  - Swapan Pati
AU  - Ashutosh Kumar
PY  - 2026
DA  - 2026/10/21
PB  - arXiv
DO  - 10.48550/arxiv.2606.00753
UR  - https://arxiv.org/abs/2606.00753
AB  - High entropy oxides are commonly associated with high configurational entropy (ΔS_conf≥ 1.61R) corresponding to five equimolar cations occupying a crystallographic sublattice. However, recent experimental observations indicate that medium-entropy compositions may also exhibit entropy-stabilized rock-salt phases, raising an important question regarding the minimum entropy required for phase stabilization. In this work, we employ a first-principles thermodynamic framework to investigate the stability of rock-salt oxides containing two to five principal cations components analogous to (Ni_0.8Cu_0.2)O, (Ni_0.6Cu_0.2Zn_0.2)O, (Ni_0.4Cu_0.2Zn_0.2Co_0.2)O, (Ni_0.2Cu_0.2Zn_0.2Co_0.2Mg_0.2)O. Density functional theory, MCSQS-based structural modeling, and finite-temperature Gibbs free-energy analysis are combined to quantify the roles of enthalpy mixing (ΔH_mix), configurational (ΔS_conf), vibrational (ΔS_vib), electronic and magnetic (ΔS_mag) contributions towards (ΔS_elec) entropy change in governing phase stability. The results show that ΔS_conf alone is not a universal descriptor of phase stability. While the two-cation system is enthalpy-stabilized but three-, four- and five-cation systems become thermodynamically stable at high-temperature due to entropy-driven reduction of the Gibbs free energy. These findings demonstrate that single-phase rock-salt oxides are not restricted to the conventional high-entropy limit and that medium-entropy compositions can also be stabilized under suitable thermodynamic conditions.
ER  -