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The rate at which a nonequilibrium system decreases its free energy is commonly ascribed to molecular relaxation processes, arising from spontaneous rearrangements at the microscopic scale. While equilibration of liquids usually requires density fluctuations at time scales quickly diverging upon cooling, growing experimental evidence indicates the presence of a different, alternative pathway of weaker temperature dependence. Such equilibration processes exhibit a temperature-invariant activation energy, on the order of 100 kJ mol −1 . Here, we identify the underlying molecular process responsible for this class of Arrhenius equilibration mechanisms with a slow mode (SAP), universally observed in the liquid dynamics of thin films. The SAP, which we show is intimately connected to high-temperature flow, can efficiently drive melts and glasses toward more stable, less energetic states. Our results show that measurements of liquid dynamics can be used to predict the equilibration rate in the glassy state.

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Confined in nanodomains, polymers crystallize much slower than in bulk due to both finite size and interfacial effects. These two factors are successfully disentangled in our phenomenological framework, which provides a measurement of the time scale of crystallization via a product of probabilities involving nucleation and of chain diffusion. In this Letter, we demonstrate that our model allows determining the Gibbs free energy of the formation of a critical size nucleus indicated by the classical nucleation theory for bulk polymer melts. In addition to that, by means of segmental mobility data and one single set of isothermal crystallization measurements at different confinement degrees, our model predicts the right temperature and thickness dependence of the crystallization time.

Neodymium doped sodium bismuth silicate glasses were prepared by the melt quench technique. Optical absorption spectra of the Nd3+ion in the present glassy systems were recorded in the UV-Vis-NIR region. Taylor series expansion method was adopted for theoretical evaluation of various crystal field parameters such as the Slater-Condon (F2,F4,F6), spin orbit and Racah parameters (E1,E2,E3). Oscillator strength and electric dipole line strength of the observed transitions were evaluated with the help of Judd-Ofelt (JO) theory. Radiative transition probability (A), total radiative transition probability (At), radiative life time (trad), branching ratios (b) and integrated absorption (sa) cross section for stimulated emission between the meta stable state 4F3/2 and 4IJ ( J= 15/2,13/2,11/2 and 9/2) levels were calculated using JO parameters. Optical basicity of the glass was found to increase with the addition of  bismuth.