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Density is the key quantity for nearly all the numerous theories of the (dynamic) glass transition of supercooled liquids and melts. As mean field quantity, it is used to describe correlations and heterogeneities between regions consisting of several molecules. In contrast, the question how density is created by the interactions (i.e., bonds) within a molecule and to its nearest neighbors is almost unexplored. To investigate this for the example of a homologous series of polyalcohols (glycerol, threitol, xylitol, and sorbitol), Fourier-Transform InfraRed (FTIR) spectroscopy is carried out in a wide range of temperatures from far above to far below the calorimetric glass transition T g . This enables us to determine the potentials and hence the bond lengths of specific intramolecular and intermolecular interactions. While the former has an expansion coefficient of (∼ 0.1 pm / 100 K) with only smooth changes, the latter shows a 30–40 times stronger response with pronounced kinks at T g . A comparison with the overall expansion based on mass density reveals that one has to separate between strong (OH ⋅ ⋅ ⋅ O) and weak (CH ⋅ ⋅ ⋅ O) intermolecular hydrogen (H)-bridges. Despite the fact that the latter dominates glassy dynamics, their expansivity is 5 times smaller than that of the weak H-bridges. It is to be expected that such heterogeneities on intramolecular and intermolecular scales are a general phenomenon in liquids and glassy systems demonstrating especially the necessity of atomistic simulations. [ABSTRACT FROM AUTHOR]

The inter- and intra-molecular interactions as they evolve in the course of glassy solidification are studied by broadband dielectric-and Fourier-transform infrared-spectroscopy for oligomeric derivatives of poly(ethylene glycol) derivatives, namely, poly(ethylene glycol) phenyl ether acrylate and poly(ethylene glycol) dibenzoate in the bulk and under confinement in nanoporous silica having mean pore diameters 4, 6, and 8 nm, with native and silanized inner surfaces. Analyzing the spectral positions and the oscillator strengths of specific IR absorption bands and their temperature dependencies enables one to trace the changes in the intra-molecular potentials and to compare it with the dielectrically determined primarily inter-molecular dynamics. Special emphasis is given to the calorimetric glass transition temperature Tg and Tαβ ≈ 1.25Tg, where characteristic changes in conformation appear, and the secondary β-relaxation merges with the dynamic glass transition (α-relaxation). Furthermore, the impact of main chain conformations, inter- and intra-molecular hydrogen bonding, and nanometric confinement on the dynamic glass transition is unraveled. [ABSTRACT FROM AUTHOR]

Glassy dynamics of polymethylphenylsiloxane (PMPS) is studied by broadband dielectric spectroscopy in one-dimensional (1D) and two-dimensional (2D) nanometric confinement; the former is realized in thin polymer layers having thicknesses down to 5 nm, and the latter in unidirectional (thickness 50 µm) nanopores with diameters varying between 4 and 8 nm. Based on the dielectric measurements carried out in a broad spectral range at widely varying temperatures, glassy dynamics is analyzed in detail in 1D and in 2D confinements with the following results: (i) the segmental dynamics (dynamic glass transition) of PMPS in 1D confinement down to thicknesses of 5 nm is identical to the bulk in the mean relaxation rate and the width of the relaxation time distribution function; (ii) additionally a well separated surface induced relaxation is observed, being assigned to adsorption and desorption processes of polymer segments with the solid interface; (iii) in 2D confinement with native inner pore walls, the segmental dynamics shows a confinement effect, i.e., the smaller the pores are, the faster the segmental dynamics; on silanization, this dependence on the pore diameter vanishes, but the mean relaxation rate is still faster than in 1D confinement; (iv) in a 2D confinement, a pronounced surface induced relaxation process is found, the strength of which increases with the decreasing pore diameter; it can be fully removed by silanization of the inner pore walls; (v) the surface induced relaxation depends on its spectral position only negligibly on the pore diameter; (vi) comparing 1D and 2D confinements, the segmental dynamics in the latter is by about two orders of magnitude faster. All these findings can be comprehended by considering the density of the polymer; in 1D it is assumed to be the same as in the bulk, hence the dynamic glass transition is not altered; in 2D it is reduced due to a frustration of packaging resulting in a higher free volume, as proven by ortho-positronium annihilation lifetime spectroscopy. [ABSTRACT FROM AUTHOR]

Charge transport and structural dynamics in a homologous pair of ammonium and phosphonium based room temperature ionic liquids (ILs) have been characterized over a wide temperature range using broadband dielectric spectroscopy and quasi-elastic light scattering spectroscopy. We have found that the ionic conductivity of the phosphonium based IL is significantly enhanced relative to the ammonium homolog, and this increase is primarily a result of a lower glass transition temperature and higher ion mobility. Additionally, these ILs exhibit pronounced secondary relaxations which are strongly influenced by the atomic identity of the cation charge center. While the secondary relaxation in the phosphonium IL has the expected Arrhenius temperature dependence characteristic of local beta relaxations, the corresponding relaxation process in the ammonium IL was found to exhibit a mildly non-Arrhenius temperature dependence in the measured temperature range--indicative of molecular cooperativity. These differences in both local and long-range molecular dynamics are a direct reflection of the subtly different inter-ionic interactions and mesoscale structures found in these homologous ILs. [ABSTRACT FROM AUTHOR]