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X-ray scattering has been used to characterize the columnar packing and the π stacking in a glass-forming discotic liquid crystal. In the equilibrium liquid state, the intensities of the scattering peaks for π stacking and columnar packing are proportional to each other, indicating concurrent development of the two orders. Upon cooling into the glassy state, the π–π distance shows a kinetic arrest with a change in the thermal expansion coefficient (TEC) from 321 to 109 ppm/K, while the intercolumnar spacing exhibits a constant TEC of 113 ppm/K. By changing the cooling rate, it is possible to prepare glasses with a wide range of columnar and π stacking orders, including zero order. For each glass, the columnar order and the π stacking order correspond to a much hotter liquid than its enthalpy and π–π distance, with the difference between the two internal (fictive) temperatures exceeding 100 K. By comparison with the relaxation map obtained by dielectric spectroscopy, we find that the δ mode (disk tumbling within a column) controls the columnar order and the π stacking order trapped in the glass, while the α mode (disk spinning about its axis) controls the enthalpy and the π–π spacing. Our finding is relevant for controlling the different structural features of a molecular glass to optimize its properties. 

Physical aging and structural recovery are the processes with which the structure of a system approaches equilibrium after some perturbation. Various methods exist, that initiate structural recovery, such as changing the temperature or applying a strong, external static field. This work is concerned with high alternating electric fields and their suitability to study structural recovery and aging. The present work demonstrates that rationalizing the nonlinear dielectric response of a supercooled liquid to high-amplitude ac-fields requires multiple fictive temperatures. This feature is in stark contrast to structural recovery after a temperature down-jump or a considerable increase in the static electric field, for which a single parameter, the fictive temperature or material time, describes the structural change. In other words, the structural recovery from a high ac-field does not adhere to time aging–time superposition, which is so characteristic of genuine aging processes. 

For a molecular glass-former, propylene glycol, we directly compare the equilibrium fluctuations, measured as “structural” relaxation in the regime of linear response, with structural recovery, i.e., field induced physical aging in the limit of a small perturbation. The two distinct correlation functions are derived from a single experiment. Because the relaxation time changes only 2% during structural recovery, no aging model is needed to analyze the results. Although being conceptually different processes, dielectric relaxation and recovery dynamics are observed to be identical for propylene glycol, whereas single-particle dynamics as seen by photon correlation spectroscopy are significantly faster. This confirms the notion that structural recovery and aging are governed by all modes observed by dielectric spectroscopy, i.e., including cross correlations, not only by single-particle dynamics. A comparison with analogous results for other materials suggests that the relation between relaxation and recovery time scales may be material specific rather than universal. 

Nonlinear dielectric measurements are an important tool to access material properties and dynamics concealed in their linear counterparts, but the available data are often intermittent and, on occasion, even contradictory. Employing and refining a recently developed technique for high ac field dielectric measurements in the static limit, we ascertain nonlinear effects in glycerol over a wide temperature range from 230 to 320 K. We find that the temperature dependence of the Piekara factor a, which quantifies the saturation effect, changes drastically around 290 K, from ∂ a/∂ T = +1.4 to −130 in units of 10 −18  V 2  m −2  K −1 . These high values of | a| quantify not only elevated dielectric saturation effects but also indicate a temperature driven increase in higher-order orientational correlations and considerable correction terms with respect to the central limit theorem. No signature of this feature can be found in the corresponding low field data. 

X-ray scattering has been used to characterize glassy itraconazole (ITZ) prepared by cooling at different rates. Faster cooling produces ITZ glasses with lower (or zero) smectic order with more sinusoidal density modulation, larger molecular spacing, and shorter lateral correlation between the rod-like molecules. We find that each glass is characterized by not one, but two fictive temperatures T_f(the temperature at which a chosen order parameter is frozen in the equilibrium liquid). The higher T_fis associated with the regularity of smectic layers and lateral packing, while the lower T_fwith the molecular spacings between and within smectic layers. This indicates that different structural features are frozen on different timescales. The two timescales for ITZ correspond to its two relaxation modes observed by dielectric spectroscopy: the slower δ mode (end-over-end rotation) is associated with the freezing of the regularity of molecular packing and the faster α mode (rotation about the long axis) with the freezing of the spacing between molecules. Our finding suggests a way to selectively control the structural features of glasses.