arXiv subjects

Vassiliy Lubchenko

Publications and source records attributed to Vassiliy Lubchenko.

31 records · Page 2Linked to original sources

arXiv2010

Electronic structure and the glass transition in pnictide and chalcogenide semiconductor alloys. Part I: The formation of the $ppσ$-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 $σ$-bonded atomic $p$-orbitals that are only weakly hybridized. Despite a large number of weak bonds, these $ppσ$-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 $ppσ$-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.

cond-mat.dis-nn↗

arXiv2010

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 $ppσ$-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.

cond-mat.dis-nn↗

arXiv2010

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 $σ$ 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.

cond-mat.dis-nn↗

arXiv2007

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 $α$-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 $β$, as extracted from $ε(ω)$ 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.

cond-mat.dis-nn↗

arXiv2006

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 $T_g$. These include: the viscosity catastrophe and heat capacity jump at $T_g$, 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 $T_g$; aging, and its correlation with fragility; the excess density of states at cryogenic temperatures due to two level tunneling systems and the Boson Peak.

cond-mat.dis-nn↗

arXiv2006

A Universal Criterion of Melting

Melting is analyzed dynamically as a problem of localization at a liquid-solid interface. A Lindemann-like criterion of melting is derived in terms of particular vibrational amplitudes, which turn out to equal a universal quotient (about one-tenth) of the molecular spacing, at the interface. The near universality of the Lindemann ratio apparently arises owing to strongly overdamped dynamics near melting, and despite the anharmonic interactions' being system-specific. A similar criterion is derived for structural displacements in the bulk of the {\em solid}, in particular the premelted layer; the criterion is no longer strictly universal, but still depends only on the harmonic properties of the solid. We further compute the dependence of the magnitude of the elemental molecular translations, in deeply supercooled fluids, on the temperature and the high frequency elastic constants. We show explicitly that the surface tension between distinct liquid states, near the glass transition of a supercooled liquid, is nearly evenly split between entropic and energetic contributions.

cond-mat.mtrl-sci↗

arXiv2005

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 Grüneisen parameter anomaly in low $T$ 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).

cond-mat.dis-nn↗

arXiv2005

The Microscopic Quantum Theory of Low Temperature Amorphous Solids

The quantum excitations in glasses have long presented a set of puzzles for condensed matter physicists. A common view is that they are largely disordered analogs of elementary excitations in crystals, supplemented by two level systems which are chemically local entities coming from disorder. A radical revision of this picture argues that the excitations in low temperature glasses are deeply connected to the energy landscape of the glass when it vitrifies: the excitations are not low excited states built on a single ground state but locally defined resonances, high in the energy spectrum of a solid. According to a semiclassical analysis, the two level systems involve resonant collective tunneling motions of around two hundred molecular units which are relics of the mosaic of cooperative motions at the glass transition temperature $T_g$. The density of states of the TLS is determined by $T_g$ and the mosaic's length scale, which is a weak function of the cooling rate. The universality of phonon scattering in insulating glasses is explained. The Boson Peak and the plateau in thermal conductivity, observed at higher temperatures, are also quantitatively understood within the picture as arising from the same cooperative motions, but now accompanied by thermal activation of the mosaic's vibrational modes. The dynamics of some of the local structural transitions have significant quantum corrections to the semiclassical picture. These corrections lead to a deviation of the heat capacity and conductivity from the standard tunneling model results and explain the anomalous time dependence of the heat capacity. Interaction between tunneling centers contributes to the large and negative value of the Grüneisen parameter often observed in glasses.

cond-mat.dis-nn↗

arXiv2004

Comment on the ``Novel Isotope Effects Observed in Polarization Echo Experiments in Glasses''

The novel isotope and magnetic effects on two level system echoes in glasses observed by Nagel et al.(Phys.Rev.Lett. 92, 245511 (2004)) provide unique experimental insight into the nature of tunneling systems in amorphous solids. We show their observations are consistent with tunneling systems being extended systems having of order 100 moving units, as predicted by theory (Phys.Rev.Lett. 87, 195901 (2001)). The numerous nuclear quadrupole interactions within a tunneling center explain the magnitude of the magnetic and frequency dependence observed in deuterated glycerol. The extended nature of two level systems explains why a small residual effect can still be observed in regular glycerol even with its low abundance of quadrupolar nuclei.

cond-mat.dis-nn↗

arXiv2004

Theory of Aging in Structural Glasses

The random first order transition theory of the dynamics of supercooled liquids is extended to treat aging phenomena in nonequilibrium structural glasses. A reformulation of the idea of ``entropic droplets'' in terms of libraries of local energy landscapes is introduced which treats in a uniform way the supercooled liquid (reproducing earlier results) and glassy regimes. The resulting microscopic theory of aging makes contact with the Nayaranaswamy-Moynihan-Tool nonlinear relaxation formalism and the Hodge-Scherer extrapolation of the Adam-Gibbs formula, but deviations from both approaches are predicted and shown to be consistent with experiment. The nonlinearity of glassy relaxation is shown to quantitatively correlate with liquid fragility. The residual nonArrhenius temperature dependence of relaxation observed in quenched glasses is explained. The broadening of relaxation spectra in the nonequilibrium glass with decreasing temperature is quantitatively predicted. The theory leads to the prediction of spatially fluctuating fictive temperatures in the long-aged glassy state, which have non-Gaussian statistics. This can give rise to ``ultra-slow'' relaxations in systems after deep quenches.

cond-mat.soft↗

arXiv2003

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 $T$ activated bevavior to a collisional transport regime at high $T$. This barrier softening explains the deviation of the relaxation times, as a function of temperature, from the simple $\log τ\propto 1/s_c$ 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.

cond-mat.dis-nn↗

arXiv2002

The Origin of the Boson Peak and the Thermal Conductivity Plateau in Low Temperature Glasses

We argue that the intrinsic glassy degrees of freedom in amorphous solids giving rise to the thermal conductivity plateau and the ``boson peak'' in the heat capacity at moderately low temperatures are directly connected to those motions giving rise to the two-level like excitations seen at still lower temperatures. These degrees of freedom can be thought of as strongly anharmonic transitions between the local minima of the glassy energy landscape that are accompanied by ripplon-like domain wall motions of the glassy mosaic structure predicted to occur at $T_g$ by the random first order transition theory. The energy spectrum of the vibrations of the mosaic depends on the glass transition temperature, the Debye frequency and the molecular length scale. The resulting spectrum reproduces the experimental low temperature Boson peak. The ``non-universality'' of the thermal conductivity plateau depends on $k_B T_g/\hbar ω_D$ and arises from calculable interactions with the phonons.

cond-mat.dis-nn↗

arXiv2001

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 $T_g$, being about 200 molecules. The phonon coupling depends on the Lindemann ratio for vitrification yielding the observed universal relation $l/λ\simeq 150$ between phonon wavelength $λ$ and mean free path $l$. Multilevel behavior is predicted to occur in the temperature range of the thermal conductivity plateau.

cond-mat.dis-nn↗