First-principles thermodynamics of Al10⁢V: An analytical treatment of localized anharmonic modes

Albuhairan, Hassan Y.; Mihalkovič, Marek; Widom, Michael

doi:10.1103/pmhq-zhl9

Title: First-principles thermodynamics of Al₁₀⁢V: An analytical treatment of localized anharmonic modes

Journal Article · Mon Nov 03 00:00:00 UTC 2025 · Physical Review. B

DOI: https://doi.org/10.1103/pmhq-zhl9 · OSTI ID:3008861

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Carnegie Mellon Univ., Pittsburgh, PA (United States); King Fahd University of Petroleum and Minerals, Dhahran (Saudi Arabia)
Slovak Academy of Sciences (Slovakia)
Carnegie Mellon Univ., Pittsburgh, PA (United States)

Many complex intermetallic structures possess cagelike environments that can host additional guest atoms. In Al₁₀⁢V, these atoms give rise to low-frequency, localized vibrations (Einstein modes) that dominate the thermodynamic response at low temperature. They become imaginary under volume expansion as temperature rises, invalidating the harmonic approximation. Here, we develop a framework to incorporate these strongly anharmonic vibrational modes into first-principles thermodynamic calculations. By explicitly modeling the cage potential and solving the associated Schrödinger equation numerically, we compute the full anharmonic free energy contribution and demonstrate its impact on the thermodynamic behavior of Al_10⁢V. This allows us to examine structures with different cage fillings and construct the Al-V phase diagram in the relevant composition range. Our results reproduce key experimental signatures, including the anomalous rise in the thermal expansion coefficient and heat capacity at low temperatures, and reveal that the presence and the extent of cage filling by guest atoms is essential to stabilizing the Al₁₀⁢V phase at elevated temperatures.

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Research Organization:: Carnegie Mellon Univ., Pittsburgh, PA (United States); Slovak Academy of Science (Slovakia)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC02-05CH11231; SC0014506

OSTI ID:: 3008861

Journal Information:: Physical Review. B, Journal Name: Physical Review. B Journal Issue: 17 Vol. 112; ISSN 2469-9969; ISSN 2469-9950

Publisher:: American Physical Society (APS)Copyright Statement

Country of Publication:: United States

Language:: English

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Title: First-principles thermodynamics of Al10⁢V: An analytical treatment of localized anharmonic modes

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Title: First-principles thermodynamics of Al₁₀⁢V: An analytical treatment of localized anharmonic modes