Dipolar Order Controls Dielectric Response of Glass-Forming Liquids.

The dielectric response of liquids reflects both reorientation of single molecular dipoles and collective modes, i.e., dipolar cross-correlations. A recent theory predicts the latter to produce an additional slow peak in the dielectric loss spectrum. Following this idea we argue that in supercooled liquids the high-frequency power law exponent of the dielectric loss ß should be correlated with the degree of dipolar order, i.e., the Kirkwood correlation factor g_{K}. This notion is confirmed for 25 supercooled liquids. While our findings support recent theoretical work the results are shown to violate the earlier Kivelson-Madden theory.

Fast vs slow physical aging of a glass forming liquid.

Using electric fields to initiate the process of physical aging has facilitated measurements of structural recovery dynamics on the time scale of milliseconds. This, however, complicates the interesting comparison with aging processes due to a temperature jump, as these are significantly slower. This study takes a step toward comparing the results of field and temperature perturbations by providing data on field-induced structural recovery of vinyl ethylene carbonate at two different time scales: 1.0 ms at 181 K and 33 s at 169 K, i.e., 4.5 decades apart. It is found that structural recovery is a factor of two slower than structural relaxation in equilibrium, with the latter determined via dielectric relaxation in the limit of linear response. The relation between recovery and relaxation dynamics remains temperature invariant across the present experimental range.

Comparing two sources of physical aging: Temperature vs electric field.

Physical aging is the process of a system evolving toward a new equilibrium, and thus the response to a change in external parameters such as temperature T, pressure p, or static electric field E. Using a static electric field has been shown to access physical aging above the glass transition temperature Tg, in the regime of milliseconds or faster, but the relation to its temperature jump counterpart has not been investigated to date. This work compares temperature and field induced physical aging in the limit of small perturbations for supercooled tributyl phosphate. It is found that both structural recovery dynamics are very similar, and that they match the collective reorientational dynamics as observed by dielectric relaxation. The results facilitate expanding the range of aging experiments to well above Tg, where a comparison with structural relaxation in equilibrium is straightforward, thus improving models of structural recovery and physical aging.

A liquid with distinct metastable structures: Supercooled butyronitrile.

The dielectric relaxation behavior of the molecular glass former butyronitrile is revisited by measuring both bulk samples cooled from the melt and samples obtained by physical vapor deposition. We find that the dielectric constant in the viscous regime of the bulk liquid is much higher than reported previously, reaching εs = 63 at T = 103 K, i.e., just above the glass transition temperature Tg = 97 K. By contrast, varying the deposition temperature and rate of vapor-deposited samples leads to dielectric constants in a range between 4.5 and 63 at T = 103 K. Values much below εs = 63 persist for thousands of seconds, where the dielectric relaxation time is about 0.1 s. The observations can be interpreted by the formation of clusters in which pair-wise anti-parallel dipole orientation is the preferred state at temperatures well below the glass transition. These non-crystalline clusters are long-lived even above Tg, where the remaining volume fraction is in the state of the equilibrium polar liquid.

Structural Relaxation and Recovery: A Dielectric Approach.

We compare structural relaxation and structural recovery dynamics for molecular glass-formers, both measured by dielectric techniques in the regime of linear responses. It is emphasized that structural recovery restores ergodicity, whereas structural relaxation or α-processes characterize fluctuations of the system in equilibrium (and thus do not involve a change of structure within experimental resolution). Evidence is provided that structural recovery is linked to rate exchange and thus is distinct from structural relaxation dynamics, even in the limit of small perturbations. As a consequence, structural recovery is somewhat slower and more exponential than the equilibrium dynamics as derived, for instance, from low field dielectric relaxation experiments. This contrasts the standard assumption inherent in models of physical aging, which assume the identity of both responses if measured in the limit of a small perturbation. Typical experiments associated with physical aging and scanning calorimetry involve nonlinear responses and are thus even more complex.