Aging vs crystallisation dynamics in hyperquenched glasses and a resolution of the water Tg controversy

The possibility of observing a glass transition in water before crystallisation occurs has been debated vigorously but inconclusively over five decades [1,2]. For two decades a glass transition at 136K [2,3] was accepted but this transition has perplexing qualities [4]. Recently it has been argued[2,5],that this assignment must be wrong. The re-assignment of Tg to temperatures above the 150K crystallisation was vigorously contested [6]. Here we use detailed anneal-and-scan studies of a hyperquenched inorganic glass, which does not crystallize on heating, to interpret the perplexing aspects of the 136K water phenomenon. We show that it is indeed linked to a glass transition, though only via a cross-over phenomenon. The thermal history that gives the same behaviour ("shadow" glass transition) in the inorganic glass is linked by crossover to a "normal" glass transition 23% higher in temperature. Thus a Tg is indeed unobservable for water, while the vitreous nature of hyperquenched glassy water is strongly supported. The shadow Tg is reproducible in the inorganic glass as it is in H2O. The observed aging dynamics are very relevant to current glass theory, particularly to dynamical heterogeneity which is seen to have an energy manifestation.Comment: 23 pages, 4 figure

A slave mode expansion for obtaining ab-initio interatomic potentials

Here we propose a new approach for performing a Taylor series expansion of the first-principles computed energy of a crystal as a function of the nuclear displacements. We enlarge the dimensionality of the existing displacement space and form new variables (ie. slave modes) which transform like irreducible representations of the space group and satisfy homogeneity of free space. Standard group theoretical techniques can then be applied to deduce the non-zero expansion coefficients a priori. At a given order, the translation group can be used to contract the products and eliminate terms which are not linearly independent, resulting in a final set of slave mode products. While the expansion coefficients can be computed in a variety of ways, we demonstrate that finite difference is effective up to fourth order. We demonstrate the power of the method in the strongly anharmonic system PbTe. All anharmonic terms within an octahedron are computed up to fourth order. A proper unitary transformation demonstrates that the vast majority of the anharmonicity can be attributed to just two terms, indicating that a minimal model of phonon interactions is achievable. The ability to straightforwardly generate polynomial potentials will allow precise simulations at length and time scales which were previously unrealizable

On the [CII]-SFR relation in high redshift galaxies

After two ALMA observing cycles, only a handful of [CII] $158\,\mu m$ emission line searches in z>6 galaxies have reported a positive detection, questioning the applicability of the local [CII]-SFR relation to high-z systems. To investigate this issue we use the Vallini et al. 2013 (V13) model, based on high-resolution, radiative transfer cosmological simulations to predict the [CII] emission from the interstellar medium of a z~7 (halo mass $M_h=1.17\times10^{11}M_{\odot}$) galaxy. We improve the V13 model by including (a) a physically-motivated metallicity (Z) distribution of the gas, (b) the contribution of Photo-Dissociation Regions (PDRs), (c) the effects of Cosmic Microwave Background on the [CII] line luminosity. We study the relative contribution of diffuse neutral gas to the total [CII] emission ($F _{diff}/F_{tot}$) for different SFR and Z values. We find that the [CII] emission arises predominantly from PDRs: regardless of the galaxy properties, $F _{diff}/F_{tot}\leq 10$% since, at these early epochs, the CMB temperature approaches the spin temperature of the [CII] transition in the cold neutral medium ($T_{CMB}\sim T_s^{CNM}\sim 20$ K). Our model predicts a high-z [CII]-SFR relation consistent with observations of local dwarf galaxies ($0.02<Z/Z_{\odot}<0.5$). The [CII] deficit suggested by actual data ($L_{CII}<2.0\times 10^7 L_{\odot}$ in BDF3299 at z~7.1) if confirmed by deeper ALMA observations, can be ascribed to negative stellar feedback disrupting molecular clouds around star formation sites. The deviation from the local [CII]-SFR would then imply a modified Kennicutt-Schmidt relation in z>6 galaxies. Alternatively/in addition, the deficit might be explained by low gas metallicities ($Z<0.1 Z_{\odot}$).Comment: 9 pages, 6 figures, replaced with the version accepted for pubblication in Ap