Vassiliy Lubchenko

Barrier softening near the onset of nonactivated 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 metastable molecular arrangements much like at a spinodal. The dynamical transition thus represents a crossover from the low T activated behavior 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 ∝1/sc 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 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 o...

The origin of the boson peak and 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 Tg 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 “nonuniversality” of the thermal conductivity plateau depends on kBTg/ℏωD and arises from calculable interactions with the phonons.

Origin of Anomalous Mesoscopic Phases in Protein Solutions

Long-living mesoscopic clusters of a dense protein liquid are a necessary kinetic intermediate for the formation of solid aggregates of native and misfolded protein molecules; in turn, these aggregates underlie physiological and pathological processes and laboratory and industrial procedures. We argue that the clusters consist of a nonequilibrium mixture of single protein molecules and long-lived complexes of proteins. The puzzling mesoscopic size of the clusters is determined by the lifetime and diffusivity of these complexes. We predict and observe a crossover of cluster dynamics to critical-like density fluctuations at high protein concentrations. We predict and experimentally confirm that cluster dynamics obey a universal, diffusion-like scaling with time and wave vector, including in the critical-like regime. Nontrivial dependencies of the cluster size and volume fraction on the protein concentration are established. Possible mechanisms of complex formation include domain swapping, hydration forces, dispersive interactions, and other, system-specific, interactions. We highlight the significance of the hydration interaction and domain swapping with regard to the ubiquity of the clusters and their sensitivity to the chemical composition of the solvent. Our findings suggest novel ways to control protein aggregation.

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/lambda approximately 150 between phonon wavelength lambda and mean free path l. Multilevel behavior is predicted to occur in the temperature range of the thermal conductivity plateau.

Ostwald-like ripening of the anomalous mesoscopic clusters in protein solutions.

Metastable clusters of mesoscopic dimensions composed of protein-rich liquid exist in protein solutions, both in the homogeneous region of the solution phase diagram and in the region supersaturated with respect to an ordered solid phase, such as crystals; in the latter region they are crucial nucleation sites for ordered solids. We monitor, using three optical techniques, the long-term evolution of the clusters in lysozyme solutions at conditions where no condensed phases, liquid or solid, are stable or present as long-lived metastable domains. We show that cluster formation is a reversible process and that the clusters are in near equilibrium with the solution, up to a capillary correction. In contrast to classical phase transformations, the solution concentration at cluster-solution equilibrium is close to its initial value; this is akin to chemical reaction equilibria and demonstrates the complex chemical composition of the clusters. However, similar to classical phase transformations, en route to full equilibration, the average cluster size grows with time following a universal law t(0.26±0.03), independent of the cluster volume fraction; the cluster size distribution is scale-invariant at all stages of cluster evolution. Despite the correspondence of these behaviors to the Lifshitz-Slyozov-Wagner (LSW) theory predictions, the cluster sizes are about 10× smaller than the LSW prediction, likely due to the complex cluster composition. The observed cluster evolution helps us to understand nucleation mysteries, such as nucleation rates lower by orders of magnitude than classical theory predictions, nucleation rate variable under steady conditions, and others.

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 nonpolymeric, nonmetallic 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 sigma of the material. The latter ratio and the ultraviolet cutoff of the theory determine the liquid configurational entropy. Our results suggest that liquids fragility depends on the Poisson ratio in a nonmonotonic way. The present ansatz provides a microscopic framework for computing the configurational entropy and relaxational spectrum of specific substances.

Theory of the structural glass transition: a pedagogical review

The random first-order transition theory of the structural glass transition is reviewed in a pedagogical fashion. The rigidity that emerges in crystals and glassy liquids is of the same fundamental origin. In both cases, it corresponds with a breaking of the translational symmetry; analogies with freezing transitions in spin systems can also be made. The common aspect of these seemingly distinct phenomena is a spontaneous emergence of the molecular field, a venerable and well-understood concept. In crucial distinction from periodic crystallisation, the free energy landscape of a glassy liquid is vastly degenerate, which gives rise to new length and time scales while rendering the emergence of rigidity gradual. We obviate the standard notion that to be mechanically stable a structure must be essentially unique; instead, we show that bulk degeneracy is perfectly allowed but should not exceed a certain value. The present microscopic description thus explains both crystallisation and the emergence of the landscape regime followed by vitrification in a unified, thermodynamics-rooted fashion. The article contains a self-contained exposition of the basics of the classical density functional theory and liquid theory, which are subsequently used to quantitatively estimate, without using adjustable parameters, the key attributes of glassy liquids, viz., the relaxation barriers, glass transition temperature, and cooperativity size. These results are then used to quantitatively discuss many diverse glassy phenomena, including the intrinsic connection between the excess liquid entropy and relaxation rates, the non-Arrhenius temperature dependence of α-relaxation, the dynamic heterogeneity, violations of the fluctuation-dissipation theorem, glass ageing and rejuvenation, rheological and mechanical anomalies, super-stable glasses, enhanced crystallisation near the glass transition, the excess heat capacity and phonon scattering at cryogenic temperatures, the Boson peak and plateau in thermal conductivity, and the puzzling midgap electronic states in amorphous chalcogenides.

Electronic structure and the glass transition in pnictide and chalcogenide semiconductor alloys. 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 [A. Zhugayevych and V. Lubchenko, J. Chem. Phys. 133, 234503 (2010)], 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.

Shear thinning in deeply supercooled melts

We compute, on a molecular basis, the viscosity of a deeply supercooled liquid at high shear rates. The viscosity is shown to decrease at growing shear rates, owing to an increase in the structural relaxation rate as caused by the shear. The onset of this non-Newtonian behavior is predicted to occur universally at a shear rate significantly lower than the typical structural relaxation rate, by approximately two orders of magnitude. This results from a large size—up to several hundred atoms—of the cooperative rearrangements responsible for mass transport in supercooled liquids and the smallness of individual molecular displacements during the cooperative rearrangements. We predict that the liquid will break down at shear rates such that the viscosity drops by approximately a factor of 30 below its Newtonian value. These phenomena are predicted to be independent of the liquids fragility. In contrast, the degree of nonexponentiality and violation of the Stokes–Einstein law, which are more prominent in fragile substances, will be suppressed by shear. The present results are in agreement with existing measurements of shear thinning in silicate melts.

Electronic structure and the glass transition in pnictide and chalcogenide semiconductor alloys. I. The formation of the ppσ-network.

Semiconductor glasses exhibit many unique optical and electronic anomalies. We have put forth a semiphenomenological scenario [A. Zhugayevych and V. Lubchenko, J. Chem. Phys. 133, 234504 (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.