220 research outputs found
Comment on "microscopic theory of network glasses"
Calorimetric experiments on network glasses provide information on the
ergodicity (landscape) temperature of supercooled liquids and can be compared
with a recent theory developed by Hall and Wolynes [PRL90, 085505 (2003)]Comment: 2 pages, 2 EPS figures RevTEX. to appear in Physical review Letter
Pressure Raman effects and internal stress in network glasses
Raman scattering from binary GexSe1-x glasses under hydrostatic pressure
shows onset of a steady increase in the frequency of modes of corner-sharing
GeSe4 tetrahedral units when the external pressure P exceeds a threshold value
Pc. The threshold pressure Pc(x) decreases with x in the 0.15 < x < 0.20 range,
nearly vanishes in the 0.20 < x < 0.25 range, and then increases in the 0.25 <
x < 1/3 range. These Pc(x) trends closely track those in the non-reversing
enthalpy, DHnr(x), near glass transitions (Tgs), and in particular, both
DHnr(x) and Pc(x) vanish in the reversibility window (0.20 < x < 0.25). It is
suggested that Pc provides a measure of stress at the Raman active units; and
its vanishing in the reversibility window suggests that these units are part of
an isostatically rigid backbone. Isostaticity also accounts for the non-aging
behavior of glasses observed in the reversibility window
A simple solvable energy landscape model that shows a thermodynamic phase transition and a glass transition
When a liquid melt is cooled, a glass or phase transition can be obtained
depending on the cooling rate. Yet, this behavior has not been clearly captured
in energy landscape models. Here a model is provided in which two key
ingredients are considered based in the landscape, metastable states and their
multiplicity. Metastable states are considered as in two level system models.
However, their multiplicity and topology allows a phase transition in the
thermodynamic limit, while a transition to the glass is obtained for fast
cooling. By solving the corresponding master equation, the minimal speed of
cooling required to produce the glass is obtained as a function of the
distribution of metastable and stable states. This allows to understand cooling
trends due to rigidity considerations in chalcogenide glasses.Comment: 4 pages (letter), 2 figure
Self-organized criticality in the intermediate phase of rigidity percolation
Experimental results for covalent glasses have highlighted the existence of a
new self-organized phase due to the tendency of glass networks to minimize
internal stress. Recently, we have shown that an equilibrated self-organized
two-dimensional lattice-based model also possesses an intermediate phase in
which a percolating rigid cluster exists with a probability between zero and
one, depending on the average coordination of the network. In this paper, we
study the properties of this intermediate phase in more detail. We find that
microscopic perturbations, such as the addition or removal of a single bond,
can affect the rigidity of macroscopic regions of the network, in particular,
creating or destroying percolation. This, together with a power-law
distribution of rigid cluster sizes, suggests that the system is maintained in
a critical state on the rigid/floppy boundary throughout the intermediate
phase, a behavior similar to self-organized criticality, but, remarkably, in a
thermodynamically equilibrated state. The distinction between percolating and
non-percolating networks appears physically meaningless, even though the
percolating cluster, when it exists, takes up a finite fraction of the network.
We point out both similarities and differences between the intermediate phase
and the critical point of ordinary percolation models without
self-organization. Our results are consistent with an interpretation of recent
experiments on the pressure dependence of Raman frequencies in chalcogenide
glasses in terms of network homogeneity.Comment: 20 pages, 18 figure
Energy landscape and rigidity
The effects of floppy modes in the thermodynamical properties of a system are
studied. From thermodynamical arguments, we deduce that floppy modes are not at
zero frequency and thus a modified Debye model is used to take into account
this effect. The model predicts a deviation from the Debye law at low
temperatures. Then, the connection between the topography of the energy
landscape, the topology of the phase space and the rigidity of a glass is
explored. As a result, we relate the number of constraints and floppy modes
with the statistics of the landscape. We apply these ideas to a simple model
for which we provide an approximate expression for the number of energy basins
as a function of the rigidity. This allows to understand certains features of
the glass transition, like the jump in the specific heat or the reversible
window observed in chalcogenide glasses.Comment: 1 text+3 eps figure
Intermediate Phases, structural variance and network demixing in chalcogenides: the unusual case of group V sulfides
We review Intermediate Phases (IPs) in chalcogenide glasses and provide a
structural interpretation of these phases. In binary group IV selenides, IPs
reside in the 2.40 < r < 2.54 range, and in binary group V selenides they shift
to a lower r, in the 2.29< r < 2.40 range. Here r represents the mean
coordination number of glasses. In ternary alloys containing equal proportions
of group IV and V selenides, IPs are wider and encompass ranges of respective
binary glasses. These data suggest that the local structural variance
contributing to IP widths largely derives from four isostatic local structures
of varying connectivity r; two include group V based quasi-tetrahedral (r =
2.29) and pyramidal (r = 2.40) units, and the other two are group IV based
corner-sharing (r = 2.40) and edge-sharing (r = 2.67) tetrahedral units.
Remarkably, binary group V (P, As) sulfides exhibit IPs that are shifted to
even a lower r than their selenide counterparts; a result that we trace to
excess Sn chains either partially (As-S) or completely (P-S) demixing from
network backbone, in contrast to excess Sen chains forming part of the backbone
in corresponding selenide glasses. In ternary chalcogenides of Ge with the
group V elements (As, P), IPs of the sulfides are similar to their selenide
counterparts, suggesting that presence of Ge serves to reign in the excess Sn
chain fragments back in the backbone as in their selenide counterparts
Kinetic glass behavior in a diffusive model
Three properties of the Edwards-Anderson model with mobile bonds are
investigated which are characteristic of kinetic glasses. First is two-time
relaxation in aged systems, where a significant difference is observed between
spin and bond autocorrelation functions. The spin subsystem does not show
two-time behavior, and the relaxation is stretched exponential. The bond
subsystem shows two-time behavior, with the first relaxation nearly exponential
and the second similar to the spin one. Second is the two-temperature behavior,
which can be tuned by bond dilution through the full range reported in the
literature. Third is the rigid-to-floppy transition, identified as a function
of bond dilution. Simple Glauber Monte Carlo evolution without extraneous
constraints reproduces the behavior of classical kinetic simulations, with the
bond (spin) degree of freedom corresponding to configurational (orientational)
disorder.Comment: 4 pages, 3 figures, minimal corrections, to appear in Phys. Rev. B
(RC
Variation of the glass transition temperature with rigidity and chemical composition
The effects of flexibility and chemical composition in the variation of the
glass transition temperature are obtained by using the Lindemann criteria, that
relates melting temperature with atomic vibrations. Using this criteria and
that floppy modes at low frequencies enhance in a considerable way the average
cuadratic displacement, we show that the consequence is a modified glass
transition temperature. This approach allows to obtain in a simple way the
empirically modified Gibbs-DiMarzio law, which has been widely used in
chalcogenide glasses to fit the changes in the glass transition temperature
with the chemical composition . The method predicts that the constant that
appears in the law depends upon the ratio of two characteristic frequencies (or
temperatures). Then, the constant for the Se-Ge-As glass is estimated by using
the experimental density of vibrational states, and the result shows a very
good agreement with the experimental fit from glass transition temperature
variation
The Thermally Reversing Window in Ternary GexPxS1-2x glasses
GexPxS1-2x glasses in the compositional range 0.05 < x < 0.19 have been
synthesized and examined in temperature modulated differential scanning
calorimetry (MDSC) and Raman scattering experiments. Trends in the
non-reversing enthalpy DHnr(x) near Tg show the term to almost vanish in the
0.090(5) < x < 0.135(5) range, and to increase by an order of magnitude at x <
0.09, and at x > 0.135. In analogy to previous results on chalcogenide glasses,
we identify compositions at x < 0.09 to be elastically floppy, those in the
0.090 0.135
to be stressed rigid. MDSC results also show the DHnr term ages in the
stressed-rigid and floppy phases but not in the intermediate phase. The
intermediate phase is viewed to be a self-organized phase of a disordered
network. It consists of at least four isostatically rigid local structures;
corner-sharing GeS4, edge-sharing GeS2, pyramidal P(S1/2)3 and
quasi-tetrahedral S=P(S1/2)3 units for which evidence comes from Raman
scattering. The latter method also shows existence of P4S7 and P4S10 molecules
in the glasses segregated from the backbone. These aspects of structure
contribute to an intermediate phase that is significantly narrower in width
than in corresponding selenide glasses.Comment: 1 PDF file has text, 9 figures and 3 table
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