Ordering Transitions in Short-Chain Alcohols

Alcohols present fascinating properties, both static and dynamic, to a large extent due to the presence of a hydrogen-bonded network. In the liquid state, hydrogen bonds (HB) are continuously forming and breaking on a timescale of 10–11 s at room temperature. Thus, these substances exhibit a rich dynamic behaviour at different time and length scales. Alcohols are considered complex systems in which structural and dynamic fluctuations in the HB network play a key role in the relaxation dynamics, as well as on the structural development. Revealing the interplay between the structural ordering and the relaxation dynamics during crystallization in short-chain alcohols is of paramount importance. One of the most powerful experimental methods to tackle this problem is dielectric spectroscopy (DS), not only because it offers information about characteristic time scales, but also because it allows obtaining information about the static properties of the system, at least in an indirect manner. In this chapter, we go through some of the most representative examples that illustrate the crystallization in short-chain alcohols by using dielectric spectroscopy, making special emphasis on those works in which dielectrics has been combined simultaneously with neutron diffraction (ND). This singular approach allows the crystal development to be tracked by means of ND, and the dynamic changes occurring in the disordered phase by DS, providing in this manner a complete picture of the structural ordering process.