Role of thermal vibrations in phase transitions

TL;DR

Thermal vibrations play a crucial role in phase transitions, and models must incorporate the Debye-Waller Factor and electron-phonon interactions to accurately reflect experimental observations.

Contribution

This paper demonstrates that neglecting thermal vibrations leads to inaccuracies in phase transition models and advocates for incorporating the Debye-Waller Factor and electron-phonon interactions.

Findings

Diffraction data prove thermal vibrations are essential in phase transition analysis.

Inclusion of thermal vibrations explains discrepancies in ordering energy, especially in Ni3V.

The Ising model fails to represent certain order-disorder transitions like in CuZn.

Abstract

All theoretical models (Heisenberg, Ising etc.) assume a negligible role for thermal vibrations in alloy and magnetic phase transitions. Analysis of diffraction data conclusively proves that this assumption is incorrect. A simple criterion emerges that theoretical models can ignore the role of thermal vibrations only if the Debye-Waller Factor is ignored in the analysis of diffraction data. Diffraction data constrain all theoretical models to incorporate the role of thermal vibrations. This conclusion is also supported by other experimental results, the effect of thermal vibrations on ordering energy that is of the same order of magnitude as ordering energy and an isotope effect on magnetic phase transitions. An electron-phonon interaction (EPI) formalism that incorporates the Debye-Waller Factor in electronic structure calculations already exists and must be adopted for a correct understanding of phase transitions as it can account for all the different experimental results mentioned above. The discrepancy between experimental and theoretical ordering energy in Ni3V is direct evidence for the role of thermal vibrations in altering ordering energy. The inter-nuclear potential energy term converges if zero point vibrations are incorporated and this method can replace the Ewald sum method. The three dimensional Ising model cannot represent order-disorder transition in beta brass, CuZn. An isotope effect is predicted for magnetic phase transitions if the transition temperature is below Debye temperature. The long range order parameter obtained from diffraction data can only be compared with predictions of models that incorporate the role of thermal vibrations and not otherwise.