Structural fluctuations and orientational glass of levoglucosan-High stability against ordering and absence of structural glass

To investigate whether a non-exponential relaxation always indicates 2-4 nm-size regions of dynamic heterogeneity, we studied the kinetic freezing and unfreezing of structural fluctuations involving the rotational modes in orientationally disordered crystal (ODIC) of levoglucosan by calorimetry. The heat capacity, C-p, of levoglucosan measured over the 203 K-463 K range shows that its low-temperature, orientationally ordered crystal (ORC) transforms to ODIC phase on heating, which then melts to a low viscosity liquid. On cooling, the melt transforms to the ODIC which then does not transform to the ORC. Instead, the ODIC supercools. Fluctuations resulting from hindered (random) rotations of levoglucosan molecules confined to the lattice sites and from their conformational changes become progressively slower on cooling and an orientational glass (O-G) forms showing the sigmoid shape decrease in C-p characteristic of structural arrest like that of a glass. On heating the O-G state, rotational fluctuations begin to contribute to C-p at To-g of 247.8 K and there is an overshoot in C-p and thermal hysteresis (characteristic of physical ageing) in the temperature range of 230-260 K. The non-exponential relaxation parameter, beta(cal), determined by fitting the C-p data to a non-exponential, nonlinear model for relaxation of a glass is 0.60, which is similar to beta(cal) found for polymers, molecular liquids, and metal-alloy melts in which Brownian diffusion occurs. Such beta(cal) < 1 are seen to indicate 2-4 nm-size dynamically heterogeneous domains in an ultraviscous liquid near the glass formation, but its value of 0.60 for ODIC levoglucosan, in which Brownian diffusion does not occur, would not indicate such domains. Despite the lack of Brownian diffusion, we discuss these findings in the potential energy landscape paradigm. Levoglucosan melt, which is believed to vitrify and to stabilize a protein's disordered structure, did not supercool even at 200 K/min cooling rate. The findings have consequences for reports on the dielectric relaxation studies that indicated that levoglucosan melt supercools to form a structural glass of T-g of similar to 245 K, and for computer simulation of its dynamics. Levoglucosan is the ninth ODIC that forms O-G. It does so more easily than the other eight. (C) 2015 AIP Publishing LLC.