Hydrogen Bonding Exchange and Supramolecular Dynamics of Monohydroxy Alcohols.

We unravel hydrogen bonding dynamics and their relationship with supramolecular relaxations of monohydroxy alcohols (MAs) at intermediate times. The rheological modulus of MAs exhibits Rouse scaling relaxation of G(t)∼t^{-1/2} switching to G(t)∼t^{-1} at time τ_{m} before their terminal time. Meanwhile, dielectric spectroscopy reveals clear signatures of new supramolecular dynamics matching with τ_{m} from rheology. Interestingly, the characteristic time τ_{m} follows an Arrhenius-like temperature dependence over exceptionally wide temperatures and agrees well with the hydrogen bonding exchange time from nuclear magnetic resonance measurements. These observations demonstrate the presence of Rouse modes and active chain swapping of MAs at intermediate times. Moreover, detailed theoretical analyses point out explicitly that the hydrogen bonding exchange truncates the Rouse dynamics of the supramolecular chains and triggers the chain-swapping processes, supporting a recently proposed living polymer model.

Surface Equilibration Mechanism Controls the Stability of a Model Codeposited Glass Mixture of Organic Semiconductors.

While previous work has identified the conditions for preparing ultrastable single-component organic glasses by physical vapor deposition (PVD), little is known about the stability of codeposited mixtures. Here, we prepared binary PVD glasses of organic semiconductors, TPD (N,N'-Bis(3-methylphenyl)-N,N'-diphenylbenzidine) and m-MTDATA (4,4',4″-Tris[phenyl(m-tolyl)amino]triphenylamine), with a 50:50 mass concentration over a wide range of substrate temperatures (Tsub). The enthalpy and kinetic stability are evaluated with differential scanning calorimetry and spectroscopic ellipsometry. Binary organic semiconductor glasses with exceptional thermodynamic and kinetic stability comparable to the most stable single-component organic glasses are obtained when deposited at Tsub = 0.78-0.90Tg (where Tg is the conventional glass transition temperature). When deposited at 0.94Tg, the enthalpy of the m-MTDATA/TPD glass equals that expected for the equilibrium liquid at that temperature. Thus, the surface equilibration mechanism previously advanced for single-component PVD glasses is also applicable for these codeposited glasses. These results provide an avenue for designing high-performance organic electronic devices.

Molecular Mechanism of the Debye Relaxation in Monohydroxy Alcohols Revealed from Rheo-Dielectric Spectroscopy.

Rheo-dielectric spectroscopy is employed to investigate the effect of external shear on Debye-like relaxation of a model monohydroxy alcohol, i.e., the 2-ethyl-1-hexanol (2E1H). Shear deformation leads to strong acceleration in the structural relaxation, the Debye relaxation, and the terminal relaxation of 2E1H. Moreover, the shear-induced reduction in structural relaxation time, τ_{α}, scales quadratically with that of Debye time, τ_{D}, and the terminal flow time, τ_{f}, suggesting a relationship of τ_{D}^{2}∼τ_{α}. Further analyses reveal τ_{D}^{2}/τ_{α} of 2E1H follows Arrhenius temperature dependence that applies remarkably well to many other monohydroxy alcohols with different molecular sizes, architectures, and alcohol types. These results cannot be understood by the prevailing transient chain model, and suggest a H-bonding breakage facilitated sub-supramolecular reorientation as the origin of Debye relaxation of monohydroxy alcohols, akin to the molecular mechanism for the terminal relaxation of unentangled "living" polymers.

Ion dynamics in pendant and backbone polymerized ionic liquids: A view from high-pressure dielectric experiments and free-volume model.

Polymerized ionic liquids (PILs) are typically single-ion conductors, where one kind of ionic species is either placed as the pendant group to the chain (pendant PILs) or directly incorporated into the polymeric backbone (backbone PILs). This paper compares the thermodynamics, ionic dynamics, and mechanical properties of pendant and backbone PILs. The results indicate that near the glass transition, the energy barrier for ion hopping is much lower for pendant PIL while the backbone PIL shows a much stronger sensitivity to pressure. At the same time, a free-volume based model was proposed here to understand the ion dynamics of both studied PILs at high-pressure conditions. The determined critical volume, quantifying the minimal volume required for ion hopping, of the pendant PIL is significantly reduced compared to the backbone PIL, which is most likely the reason for the enhanced ionic conductivity of the pendant PIL near the glass transition. We found that the proposed model is equivalent to the commonly used pressure counterpart of the Vogel-Fulcher-Tammann equation.

Pressure-induced liquid-liquid transition in a family of ionic materials.

Liquid-liquid transition (LLT) between two disordered phases of single-component material remains one of the most intriguing physical phenomena. Here, we report a first-order LLT in a series of ionic liquids containing trihexyl(tetradecyl)phosphonium cation [P666,14]+ and anions of different sizes and shapes, providing an insight into the structure-property relationships governing LLT. In addition to calorimetric proof of LLT, we report that ion dynamics exhibit anomalous behavior during the LLT, i.e., the conductivity relaxation times (τσ) are dramatically elongated, and their distribution becomes broader. This peculiar behavior is induced by isobaric cooling and isothermal compression, with the τσ(TLL,PLL) constant for a given system. The latter observation proves that LLT, in analogy to liquid-glass transition, has an isochronal character. Finally, the magnitude of discontinuity in a specific volume at LLT was estimated using the Clausius-Clapeyron equation.

Complex Reorientation Dynamics of Sizable Glass-Formers with Polar Rotors Revealed by Dielectric Spectroscopy.

We present the results of dielectric measurements for three sizable glass-formers with identical nonpolar cores linked to various dipole-labeled rotors that shed new light on the picture of reorientation of anisotropic systems with significant moment of inertia revealed by broadband dielectric spectroscopy. The dynamics of sizable glass-formers formed by partially rigid molecular cores linked to small polar rotors in many respects differs from that of typical glass-formers. For instance, the extraordinarily large prefactors (τ0 > 10-12 s) in the Vogel-Fulcher-Tammann equation were found. The rich and highly diverse relaxation pattern was governed by the location of a dipole, its ability to rotate freely, and the degree of coupling to the motion of the entire sizable system.

Magnitude of Dynamically Correlated Molecules as an Indicator for a Dynamical Crossover in Ionic Liquids.

In this work, we show how the structure and intermolecular interactions affect the dynamic heterogeneity of aprotic ionic liquids. Using calorimetric data for 30 ionic samples, we examine the influence of the strength of van der Waals and Coulombic interactions on dynamic heterogeneity. We show that the dynamic length scale of spatially heterogeneous dynamics decreases significantly with decreasing intermolecular distances. Additionally, we assume that the magnitude of the number of dynamically correlated molecules at the liquid-glass transition temperature can be treated as an indicator for a dynamical crossover.

Thorough studies of tricyanomethanide-based ionic liquids - the influence of alkyl chain length of the cation.

The glassy, supercooled, and normal liquid states of the 1-alkyl-3-methylimidazolium tricyanomethanide series [CnC1im][TCM] (n = 2, 4, 6, 8, and 16) were investigated by dielectric and mechanical (rheological) experiments supplemented by X-ray diffraction. The conductivity relaxation was found to be accompanied by a pronounced secondary relaxation. However, based on ambient and high-pressure results as well as the coupling model, we assumed that the latter one can not be classified as Johari-Goldstein relaxation. Moreover, the studies on the nanoscale organization of ionic liquids indicated that 1-alkyl-3-methylimidazolium tricyanomethanide ILs begin to form nanoscale aggregates when the alkyl chain of the cation has six carbon atoms.

The behavior of conductivity dynamic modulus and its connection to thermodynamic bulk modulus in ionic liquids.

In this paper, we investigate the interplay between the dynamics and thermodynamics of aprotic ionic liquids in the supercooled and normal liquid states. For this purpose, the conductivity dynamic modulus Mσp-T, being defined as the ratio of activation energy (Ep) and activation volume (VT), and its relation to bulk modulus BT under isobaric and isothermal conditions is examined. We found that both isobaric cooling and isothermal compression lead to an increase in Mσp-T. Specifically, Mσp-T(P)T rises linearly similar to BT. Consequently, a direct linear relationship between Mσp-T(P)T and BT is established under isothermal conditions.

Access to Thermodynamic and Viscoelastic Properties of Poly(ionic liquid)s Using High-Pressure Conductivity Measurements.

In this paper, we examine the transport properties of a 1,2,3-triazolium-based poly(ionic liquid) (PIL) at ambient and elevated pressure up to 475 MPa. We show that the isothermal and isobaric conductivity measurements analyzed in the 3D plane give a unique possibility to estimate the thermodynamic (isothermal compressibility and thermal expansion coefficient) properties for PILs having a charge transport fully controlled by viscosity. This result, providing a direct connection between thermodynamic and dynamic properties of PILs, is of significant importance for both material scientists and practical applications.