96 research outputs found
Barrier Softening near the onset of Non-Activated Transport in Supercooled Liquids: Implications for Establishing Detailed Connection between Thermodynamic and Kinetic Anomalies in Supercooled Liquids
According to the Random First Order Transition (RFOT) theory of glasses, the
barriers for activated dynamics in supercooled liquids vanish as the
temperature of a viscous liquid approaches the dynamical transition temperature
from below. This occurs due to a decrease of the surface tension between local
meta-stable molecular arrangements much like at a spinodal. The dynamical
transition thus represents a crossover from the low activated bevavior to a
collisional transport regime at high . This barrier softening explains the
deviation of the relaxation times, as a function of temperature, from the
simple dependence at the high viscosity to a
mode-mode coupling dominated result at lower viscosity. By calculating the
barrier softening effects, the RFOT theory provides a {\em unified} microscopic
way to interpret structural relaxation data for many distinct classes of
structural glass formers over the measured temperature range. The theory also
provides an unambiguous procedure to determine the size of dynamically
cooperative regions in the presence of barrier renormalization effects using
the experimental temperature dependence of the relaxation times and the
configurational entropy data. We use the RFOT theory framework to discuss data
for tri-naphthyl benzene, salol, propanol and silica as representative systems.Comment: Submitted to J. Chem. Phy
Electronic structure and the glass transition in pnictide and chalcogenide semiconductor alloys. Part II: The intrinsic electronic midgap states
We propose a structural model that treats in a unified fashion both the
atomic motions and electronic excitations in quenched melts of pnictide and
chalcogenide semiconductors. In Part I (submitted to J. Chem. Phys.), we argued
these quenched melts represent aperiodic -networks that are highly
stable and, at the same time, structurally degenerate. These networks are
characterized by a continuous range of coordination. Here we present a
systematic way to classify these types of coordination in terms of discrete
coordination defects in a parent structure defined on a simple cubic lattice.
We identify the lowest energy coordination defects with the intrinsic midgap
electronic states in semiconductor glasses, which were argued earlier to cause
many of the unique optoelectronic anomalies in these materials. In addition,
these coordination defects are mobile and correspond to the transition state
configurations during the activated transport above the glass transition. The
presence of the coordination defects may account for the puzzling discrepancy
between the kinetic and thermodynamic fragility in chalcogenides. Finally, the
proposed model recovers as limiting cases several popular types of bonding
patterns proposed earlier, including: valence-alternation pairs, hypervalent
configurations, and homopolar bonds in heteropolar compounds.Comment: 17 pages, 15 figures, revised version, final version to appear in J.
Chem. Phy
Stress distribution and the fragility of supercooled melts
We formulate a minimal ansatz for local stress distribution in a solid that
includes the possibility of strongly anharmonic short-length motions. We
discover a broken-symmetry metastable phase that exhibits an aperiodic,
frozen-in stress distribution. This aperiodic metastable phase is characterized
by many distinct, nearly degenerate configurations. The activated transitions
between the configurations are mapped onto the dynamics of a long range
classical Heisenberg model with 6-component spins and anisotropic couplings. We
argue the metastable phase corresponds to a deeply supercooled non-polymeric,
non-metallic liquid, and further establish an order parameter for the
glass-to-crystal transition. The spin model itself exhibits a continuous range
of behaviors between two limits corresponding to frozen-in shear and uniform
compression/dilation respectively. The two regimes are separated by a
continuous transition controlled by the anisotropy in the spin-spin
interaction, which is directly related to the Poisson ratio of the
material. The latter ratio and the ultra-violet cutoff of the theory determine
the liquid configurational entropy. Our results suggest that liquid's fragility
depends on the Poisson ratio in a non-monotonic way. The present ansatz
provides a microscopic framework for computing the configurational entropy and
relaxational spectrum of specific substances.Comment: 11 pages, 5 figures, Final version published in J Phys Chem
Electronic structure and the glass transition in pnictide and chalcogenide semiconductor alloys. Part I: The formation of the -network
Semiconductor glasses exhibit many unique optical and electronic anomalies.
We have put forth a semi-phenomenological scenario (J. Chem. Phys. 132, 044508
(2010)) in which several of these anomalies arise from deep midgap electronic
states residing on high-strain regions intrinsic to the activated transport
above the glass transition. Here we demonstrate at the molecular level how this
scenario is realized in an important class of semiconductor glasses, namely
chalcogen and pnictogen containing alloys. Both the glass itself and the
intrinsic electronic midgap states emerge as a result of the formation of a
network composed of -bonded atomic -orbitals that are only weakly
hybridized. Despite a large number of weak bonds, these -networks are
stable with respect to competing types of bonding, while exhibiting a high
degree of structural degeneracy. The stability is rationalized with the help of
a hereby proposed structural model, by which -networks are
symmetry-broken and distorted versions of a high symmetry structure. The latter
structure exhibits exact octahedral coordination and is fully
covalently-bonded. The present approach provides a microscopic route to a fully
consistent description of the electronic and structural excitations in vitreous
semiconductors.Comment: 22 pages, 17 figures, revised version, final version to appear in J.
Chem. Phy
The Ultimate Fate of Supercooled Liquids
In recent years it has become widely accepted that a dynamical length scale
{\xi}_{\alpha} plays an important role in supercooled liquids near the glass
transition. We examine the implications of the interplay between the growing
{\xi}_{\alpha} and the size of the crystal nucleus, {\xi}_M, which shrinks on
cooling. We argue that at low temperatures where {\xi}_{\alpha} > {\xi}_M a new
crystallization mechanism emerges enabling rapid development of a large scale
web of sparsely connected crystallinity. Though we predict this web percolates
the system at too low a temperature to be easily seen in the laboratory, there
are noticeable residual effects near the glass transition that can account for
several previously observed unexplained phenomena of deeply supercooled liquids
including Fischer clusters, and anomalous crystal growth near T_g
The Intrinsic Quantum Excitations of Low Temperature Glasses
Several puzzling regularities concerning the low temperature excitations of
glasses are quantitatively explained by quantizing domain wall motions of the
random first order glass transition theory. The density of excitations agrees
with experiment and scales with the size of a dynamically coherent region at
, being about 200 molecules. The phonon coupling depends on the Lindemann
ratio for vitrification yielding the observed universal relation between phonon wavelength and mean free path .
Multilevel behavior is predicted to occur in the temperature range of the
thermal conductivity plateau.Comment: 4 pages, submitted to PR
Capturing the essence of folding and functions of biomolecules using Coarse-Grained Models
The distances over which biological molecules and their complexes can
function range from a few nanometres, in the case of folded structures, to
millimetres, for example during chromosome organization. Describing phenomena
that cover such diverse length, and also time scales, requires models that
capture the underlying physics for the particular length scale of interest.
Theoretical ideas, in particular, concepts from polymer physics, have guided
the development of coarse-grained models to study folding of DNA, RNA, and
proteins. More recently, such models and their variants have been applied to
the functions of biological nanomachines. Simulations using coarse-grained
models are now poised to address a wide range of problems in biology.Comment: 37 pages, 8 figure
Holographic Vitrification
We establish the existence of stable and metastable stationary black hole
bound states at finite temperature and chemical potentials in global and planar
four-dimensional asymptotically anti-de Sitter space. We determine a number of
features of their holographic duals and argue they represent structural
glasses. We map out their thermodynamic landscape in the probe approximation,
and show their relaxation dynamics exhibits logarithmic aging, with aging rates
determined by the distribution of barriers.Comment: 100 pages, 25 figure
Detection of hidden structures for arbitrary scales in complex physical systems
Recent decades have experienced the discovery of numerous complex materials. At the root of the complexity underlying many of these materials lies a large number of contending atomic- and largerscale configurations. In order to obtain a more detailed understanding of such systems, we need tools that enable the detection of pertinent structures on all spatial and temporal scales. Towards this end, we suggest a new method that applies to both static and dynamic systems which invokes ideas from network analysis and information theory. Our approach efficiently identifies basic unit cells, topological defects, and candidate natural structures. The method is particularly useful where a clear definition of order is lacking, and the identified features may constitute a natural point of departure for further analysis
Inference of hidden structures in complex physical systems by multi-scale clustering
We survey the application of a relatively new branch of statistical
physics--"community detection"-- to data mining. In particular, we focus on the
diagnosis of materials and automated image segmentation. Community detection
describes the quest of partitioning a complex system involving many elements
into optimally decoupled subsets or communities of such elements. We review a
multiresolution variant which is used to ascertain structures at different
spatial and temporal scales. Significant patterns are obtained by examining the
correlations between different independent solvers. Similar to other
combinatorial optimization problems in the NP complexity class, community
detection exhibits several phases. Typically, illuminating orders are revealed
by choosing parameters that lead to extremal information theory correlations.Comment: 25 pages, 16 Figures; a review of earlier work
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