Non-Linear Arrhenius Behavior of Self-Diffusion in $\beta$-Ti and Mo

TL;DR

This study explains the non-Arrhenius temperature dependence of self-diffusion in bcc metals Mo and β-Ti using first-principles calculations, highlighting the role of anharmonicity from thermal expansion.

Contribution

It introduces a novel methodology combining quasiharmonic transition state theory and a modified Debye approach to accurately model diffusion in mechanically unstable crystals.

Findings

Thermal expansion significantly influences diffusion prefactors.

Anharmonicity from thermal expansion causes non-Arrhenius behavior.

Methodology aligns well with experimental data.

Abstract

While anomalous diffusion coefficients with non-Arrhenius like temperature dependence are observed in a number of metals, a conclusive comprehensive framework of explanation has not been brought forward to date. Here, we use first-principles calculations based on density functional theory to calculate self-diffusion coefficients in the bcc metals Mo and $\beta$-Ti by coupling quasiharmonic transition state theory and large displacement phonon calculations and show that anharmonicity from thermal expansion is the major reason for the anomalous temperature dependence. We use a modified Debye approach to quantify the thermal expansion over the entire temperature range and introduce a method to relax the vacancy structure in a mechanically unstable crystal such as $\beta$-Ti. Thermal expansion is found to weakly affect the activation enthalpy but has a strong effect on the prefactor of the diffusion coefficient, reproducing the non-linear, non-Arrhenius "anomalous" self-diffusion in both bcc systems with good agreement between calculation and experiment. The proposed methodology is general and simple enough to be applicable to other mechanically unstable crystals.