A Dynamical Approach to the \(\alpha \)–\(\beta \) Displacive Transition of Quartz

Abstract

The problem of displacive phase transitions (by which crystals pass on heating from a less symmetric to a more symmetric form) is investigated through numerical integration of the Newton equations of motion for a realistic model, in the paradigmatic case of quartz. Usually such transitions are discussed in terms of the positions of the atoms, while the role of normal modes is emphasized here. The key preliminary property established, in agreement with the indications given by Landau in his thermodynamic-like approach, is that four well definite modes are sufficient to describe the transition, the remaining modes just acting as a noise. The main result is then that such four modes constitute a closed Hamiltonian subsystem presenting an effective potential parametrically dependent on specific energy. The effective potential is actually computed, through (appropriately defined) time-averages of the accelerations of the relevant modes, and is found to describe, as energy is varied, a pitchfork bifurcation, once more confirming in dynamical terms the Landau result. The effective potential also allows one to advance a possible explanation of the “soft mode” phenomenon, namely the occuring, in the Raman spectrum, of a peak whose frequency depends on temperature and vanishes at the transition.