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arXiv · 2610.11882

Beyond special quasirandom structures: free energies from energy cumulants

Yann L. Müller·Anirudh Raju Natarajan
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Abstract

Predicting the finite-temperature stability of a disordered phase requires its free energy. It is traditionally approximated by combining the energy of a special quasirandom structure (a small cell mimicking a random alloy) with the ideal configurational entropy. This approximation neglects the short-range order that develops on cooling. In this study, we show that the conventional approximation is the first term of an infinite expansion of the free energy in energy cumulants. Higher-order cumulants are estimated from energies of random arrangements, without Monte Carlo or molecular dynamics. In a nine-element refractory system, adding the second cumulant reduced free energy errors by about an order of magnitude. The expansion gives phase diagrams with order--disorder transitions, defect concentrations, and short-range order. To demonstrate its utility, we used a foundation interatomic potential to screen lithium-excess rocksalt oxides across 26 elements for synthesizable disordered phases rich in the Li$_4$ clusters needed for lithium percolation. The approach applies to any lattice and chemistry, and brings disordered phases within reach of routine screening.

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Yann L. Müller, Anirudh Raju Natarajan. 2026-10-08. Beyond special quasirandom structures: free energies from energy cumulants. https://arxiv.org/abs/2610.11882

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