TRANSLATION-ROTATION COUPLING, PHASE-TRANSITIONS, AND ELASTIC PHENOMENA IN ORIENTATIONALLY DISORDERED CRYSTALS

Many of the properties of orientationally disordered crystals are profoundly affected by the coupling (known as translation-rotation coupling) between translation displacements and molecular orientation. The consequences of translation-rotation coupling depend on molecular and crystal symmetry, and vary throughout the Brillouin zone. One result is an indirect coupling between the orientations of different molecules, which plays an important role in the order/disorder phase transition, especially in ionic orientationally disordered crystals. Translation-rotation coupling also leads to softening of elastic constants and affects phonon spectra. This article describes the theory of the coupling from the point of view of the microscopic Hamiltonian and the resulting Landau free energy. Considerable emphasis is placed on the restrictions due to symmetry as these are universal and can be used to help one's qualitative understanding of experimental observations. The application of the theory to phase transitions is described. The softening of elastic constants is discussed and shown to be universal. However, anomalies associated with the order/disorder phase transition are shown to be restricted to cases in which the symmetry of the order parameter satisfies certain conditions. Dynamic effects on phonon spectra are described and finally the recently observed dielectric behavior of ammonium compounds is discussed. Throughout the article examples from published experiments are used to illustrate the application of the theory including well known examples such as the alkali metal cyanides and more recently discovered orientationally disordered crystals such as the fullerite, C60.