Vibrational Entropy of Crystalline Solids from Covariance of Atomic Displacements

Huang, Yang; Widom, Michael

doi:10.3390/e24050618

Vibrational Entropy of Crystalline Solids from Covariance of Atomic Displacements

Journal Article · Thu Apr 28 04:00:00 EDT 2022 · Entropy

DOI:https://doi.org/10.3390/e24050618· OSTI ID:1865698

Huang, Yang;

The vibrational entropy of a solid at finite temperature is investigated from the perspective of information theory. Ab initio molecular dynamics (AIMD) simulations generate ensembles of atomic configurations at finite temperature from which we obtain the N-body distribution of atomic displacements, ρN. We calculate the information-theoretic entropy from the expectation value of lnρN. At a first level of approximation, treating individual atomic displacements independently, our method may be applied using Debye–Waller B-factors, allowing diffraction experiments to obtain an upper bound on the thermodynamic entropy. At the next level of approximation we correct the overestimation through inclusion of displacement covariances. We apply this approach to elemental body-centered cubic sodium and face-centered cubic aluminum, showing good agreement with experimental values above the Debye temperatures of the metals. Below the Debye temperatures, we extract an effective vibrational density of states from eigenvalues of the covariance matrix, and then evaluate the entropy quantum mechanically, again yielding good agreement with experiment down to low temperatures. Our method readily generalizes to complex solids, as we demonstrate for a high entropy alloy. Further, our method applies in cases where the quasiharmonic approximation fails, as we demonstrate by calculating the HCP/BCC transition in Ti.

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Sponsoring Organization:: USDOE

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

OSTI ID:: 1865698

Alternate ID(s):: OSTI ID: 1865900

Journal Information:: Entropy, Journal Name: Entropy Journal Issue: 5 Vol. 24; ISSN ENTRFG; ISSN 1099-4300

Publisher:: MDPI AGCopyright Statement

Country of Publication:: Switzerland

Language:: English

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