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Main Authors: Hashimoto, Kota, Tanaka, Tomonori, Gohda, Yoshihiro
Format: Preprint
Published: 2024
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Online Access:https://arxiv.org/abs/2405.14823
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author Hashimoto, Kota
Tanaka, Tomonori
Gohda, Yoshihiro
author_facet Hashimoto, Kota
Tanaka, Tomonori
Gohda, Yoshihiro
contents We propose a method to evaluate the Gibbs free energy from constant-volume first-principles phonon calculations. The volume integral of the pressure is performed by determining the volume and the bulk modulus in equilibrium at finite temperatures, where the pressure and its volume derivative are evaluated utilizing first-principles calculations of the Grüneisen parameter without varying the volume. We validate our method for fcc Al by comparing with the conventional quasiharmonic approximation. Furthermore, we integrate our method with self-consistent phonon theory and apply it to calculations for bcc Ti, hcp Ti, and tetragonal ZrO$_2$. We demonstrate the accuracy and computational efficiency of our method by comparing results with those obtained from directly volume-varied self-consistent phonon calculations. In all cases, our method accurately evaluates the free energy change due to thermal expansion using only constant-volume phonon calculations.
format Preprint
id arxiv_https___arxiv_org_abs_2405_14823
institution arXiv
publishDate 2024
record_format arxiv
spellingShingle Efficient first-principles approach to Gibbs free energy with thermal expansion
Hashimoto, Kota
Tanaka, Tomonori
Gohda, Yoshihiro
Materials Science
We propose a method to evaluate the Gibbs free energy from constant-volume first-principles phonon calculations. The volume integral of the pressure is performed by determining the volume and the bulk modulus in equilibrium at finite temperatures, where the pressure and its volume derivative are evaluated utilizing first-principles calculations of the Grüneisen parameter without varying the volume. We validate our method for fcc Al by comparing with the conventional quasiharmonic approximation. Furthermore, we integrate our method with self-consistent phonon theory and apply it to calculations for bcc Ti, hcp Ti, and tetragonal ZrO$_2$. We demonstrate the accuracy and computational efficiency of our method by comparing results with those obtained from directly volume-varied self-consistent phonon calculations. In all cases, our method accurately evaluates the free energy change due to thermal expansion using only constant-volume phonon calculations.
title Efficient first-principles approach to Gibbs free energy with thermal expansion
topic Materials Science
url https://arxiv.org/abs/2405.14823