159 research outputs found
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
Charge and momentum transfer in supercooled melts: Why should their relaxation times differ?
The steady state values of the viscosity and the intrinsic ionic-conductivity
of quenched melts are computed, in terms of independently measurable
quantities. The frequency dependence of the ac dielectric response is
estimated. The discrepancy between the corresponding characteristic relaxation
times is only apparent; it does not imply distinct mechanisms, but stems from
the intrinsic barrier distribution for -relaxation in supercooled
fluids and glasses. This type of intrinsic ``decoupling'' is argued not to
exceed four orders in magnitude, for known glassformers. We explain the origin
of the discrepancy between the stretching exponent , as extracted from
and the dielectric modulus data. The actual width of the
barrier distribution always grows with lowering the temperature. The contrary
is an artifact of the large contribution of the dc-conductivity component to
the modulus data. The methodology allows one to single out other contributions
to the conductivity, as in ``superionic'' liquids or when charge carriers are
delocalized, implying that in those systems, charge transfer does not require
structural reconfiguration.Comment: submitted to J Chem Phy
Electrodynamics of Amorphous Media at Low Temperatures
Amorphous solids exhibit intrinsic, local structural transitions, that give
rise to the well known quantum-mechanical two-level systems at low
temperatures. We explain the microscopic origin of the electric dipole moment
of these two-level systems: The dipole emerges as a result of polarization
fluctuations between near degenerate local configurations, which have nearly
frozen in at the glass transition. An estimate of the dipole's magnitude, based
on the random first order transition theory, is obtained and is found to be
consistent with experiment. The interaction between the dipoles is estimated
and is shown to contribute significantly to the Gr\"{u}neisen parameter anomaly
in low glasses. In completely amorphous media, the dipole moments are
expected to be modest in size despite their collective origin. In partially
crystalline materials, however, very large dipoles may arise, possibly
explaining the findings of Bauer and Kador, J. Chem. Phys. {\bf 118}, 9069
(2003).Comment: Submitted for publication; April 27, 2005 versio
Theory of Structural Glasses and Supercooled Liquids
We review the Random First Order Transition Theory of the glass transition,
emphasizing the experimental tests of the theory. Many distinct phenomena are
quantitatively predicted or explained by the theory, both above and below the
glass transition temperature . These include: the viscosity catastrophe
and heat capacity jump at , and their connection; the non-exponentiality
of relaxations and their correlation with the fragility; dynamic heterogeneity
in supercooled liquids owing to the mosaic structure; deviations from the
Vogel-Fulcher law, connected with strings or fractral cooperative
rearrangements; deviations from the Stokes-Einstein relation close to ;
aging, and its correlation with fragility; the excess density of states at
cryogenic temperatures due to two level tunneling systems and the Boson Peak.Comment: submitted to Ann. Rev. Phys. Che
Aging, jamming, and the limits of stability of amorphous solids
Apart from not having crystallized, supercooled liquids can be considered as
being properly equilibrated and thus can be described by a few thermodynamic
control variables. In contrast, glasses and other amorphous solids can be
arbitrarily far away from equilibrium and require a description of the history
of the conditions under which they formed. In this paper we describe how the
locality of interactions intrinsic to finite-dimensional systems affects the
stability of amorphous solids far off equilibrium. Our analysis encompasses
both structural glasses formed by cooling and colloidal assemblies formed by
compression. A diagram outlining regions of marginal stability can be adduced
which bears some resemblance to the quasi-equilibrium replica meanfield theory
phase diagram of hard sphere glasses in high dimensions but is distinct from
that construct in that the diagram describes not true phase transitions but
kinetic transitions that depend on the preparation protocol. The diagram
exhibits two distinct sectors. One sector corresponds to amorphous states with
relatively open structures, the other to high density, more closely-packed
ones. The former transform rapidly owing to there being motions with no free
energy barriers; these motions are string-like locally. In the dense region,
amorphous systems age via compact activated reconfigurations. The two regimes
correspond, in equilibrium, to the collisional or uniform liquid and the so
called landscape regime, respectively. These are separated by a spinodal line
of dynamical crossovers. Owing to the rigidity of the surrounding matrix in the
landscape, high-density part of the diagram, a sufficiently rapid pressure
quench adds compressive energy which also leads to an instability toward
string-like motions with near vanishing barriers. (SEE REST OF ABSTRACT IN THE
ARTICLE.)Comment: submitted to 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
Comparison and Uncertainty Quantification of Two-Fluid Models forBubbly Flows with NEPTUNE_CFD and STAR-CCM+
International audienceThe nuclear industry is interested in better understanding the behavior of turbulent boiling flowsand in using modern computational tools for the design and analysis of advanced fuels and reactorsand for simulation and study of mitigation strategies in accident scenarios. Such interests serve asdrivers for the advancement of the 3-dimensional multiphase Computational Fluid Dynamicsapproach. A pair of parallel efforts have been underway in Europe and in the United States, theNEPTUNE and CASL programs respectively, that aim at delivering advanced simulation tools thatwill enable improved safety and economy of operations of the reactor fleet. Results from acollaboration between these two efforts, aimed at advancing the understanding of multiphaseclosures for pressurized water reactor (PWR) application, are presented. Particular attention is paidto the assessment and analysis of the different physical models implemented in NEPTUNE_CFDand STAR-CCM+ codes used in the NEPTUNE and the CASL programs respectively, forapplication to turbulent two-phase bubbly flows. The experiments conducted by Liu and Bankoff(Liu, 1989; Liu and Bankoff 1993a and b) are selected for benchmarking, and predictions from thetwo codes are presented for a broad range of flow conditions and with void fractions varyingbetween 0 and 50percent. Comparison of the CFD simulations and experimental measurements revealsthat a similar level of accuracy is achieved in the two codes. The differences in both sets of closuremodels are analyzed, and their capability to capture the main features of the flow over a wide rangeof experimental conditions are discussed. This analysis paves the way for future improvements ofexisting two-fluid models. The benchmarks are further leveraged for a systematic study of thepropagation of model uncertainties. This provides insights into mechanisms that lead to complexinteractions between individual closures (of the different phenomena) in the multiphase CFDapproach. As such, it is seen that the multi-CFD-code approach and the principled uncertaintyquantification approach are both of great value in assessing the limitations and the level of maturityof multiphase hydrodynamic closures
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
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