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 $\log \tau \propto 1/s_c$ 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.Comment: Submitted to 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 $\sigma$ 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 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 $pp\sigma$-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

Universality in Glassy Low-Temperature Physics

We propose a microscopic translationally invariant glass model which exhibits two level tunneling systems with a broad range of asymmetries and barrier heights in its glassy phase. Their distribution is qualitatively different from what is commonly assumed in phenomenological models, in that symmetric tunneling systems are systematically suppressed. Still, the model exhibits the usual glassy low-temperature anomalies. Universality is due to the collective origin of the glassy potential energy landscape. We obtain a simple explanation also for the mysterious {\em quantitative} universality expressed in the unusually narrow universal glassy range of values for the internal friction plateau.Comment: 4 pages, 5 figures, uses RevTeX

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 ppσpp\sigma-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 $\sigma$-bonded atomic $p$-orbitals that are only weakly hybridized. Despite a large number of weak bonds, these $pp\sigma$-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 $pp\sigma$-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

What are the interactions in quantum glasses?

The form of the low-temperature interactions between defects in neutral glasses is reconsidered. We analyse the case where the defects can be modelled either as simple 2-level tunneling systems, or tunneling rotational impurities. The coupling to strain fields is determined up to 2nd order in the displacement field. It is shown that the linear coupling generates not only the usual $1/r^3$ Ising-like interaction between the rotational tunneling defect modes, which cause them to freeze around a temperature $T_G$, but also a random field term. At lower temperatures the inversion symmetric tunneling modes are still active - however the coupling of these to the frozen rotational modes, now via the 2nd-order coupling to phonons, generates another random field term acting on the inversion symmetric modes (as well as shorter-range $1/r^5$ interactions between them). Detailed expressions for all these couplings are given.Comment: 12 pages, 2 figures. Minor modifications, published versio

Лазерные фазовые дальномеры: пути повышения точности

   Scientific and technological progress in the field of geodetic and industrial measurements in terms of the use of laser rangefinders operating in ranges up to 5000 meters has led to a reduction in the error of such measuring instruments over the past ten years by two or more times. Such rapid development of high-precision rangefinder technologies has led to a significant revision of the requirements for their metrological support, as well as to the need to develop a new generation of length standards, the stock of metrological accuracy of which would provide an assessment of the metrological characteristics of all types of existing and promising length measuring instruments with a laser rangefinder. To solve this problem, the Institute’s staff conducted research within the framework of a number of thematic research and development works in terms of developing the appearance of a new generation of length standards operating in the range up to 5000 meters in an open atmosphere. Within the framework of this article, one of the developed models of a high-precision complex of measuring instruments for length and coordinate increments is considered, which is a serial high-precision laser phase light meter, modified by the institute’s staff in terms of the system for receiving and processing measuring signals. At the same time, in order to increase the accuracy of length measurements using the developed range finder layout, it is proposed to investigate ways to reduce the errors of the model components of the boundaries of its error. To ensure the smallest error in determining the hardware correction of the rangefinder layout, it is proposed to use funds from the state primary special standard of the unit of length. As promising ways to reduce the error in determining the phase difference of signals, it is proposed to use digital recording and signal processing devices that implement a method for calculating the phase difference of signals by mathematically processing the recorded data using a specially developed computational algorithm based on Fourier analysis. For the most accurate determination of the values of the pulse repetition frequency of signals and the values of the speed of light on the measured track, it is proposed to improve the means of determining these indicators. The use of the proposed methods to improve the accuracy of measuring the length of laser phase rangefinders allows you to provide the necessary margin of metrological accuracy.   Научно-технический прогресс в сфере геодезических и промышленных измерений в части использования лазерных дальномеров, работающих в диапазонах до 5 000 метров, привел к уменьшению погрешности выше перечисленных средств измерений за последние десять лет в два и более раза. Следствием такого стремительного развития технологий высокоточной дальнометрии стал значительный пересмотр требований по их метрологическому обеспечению, а также необходимость разработки нового поколения эталонов длины, запас метрологической точности которых обеспечивал бы оценку метрологических характеристик всех типов существующих и перспективных средств измерений длины, имеющих в своем составе лазерный светодальномер. Для решения этой задачи авторами в рамках ряда тематических научно-исследовательских опытно-конструкторских работ проводились исследования с целью разработки нового поколения эталонов длины, работающих в диапазоне до 5 000 метров, в условиях открытой атмосферы. В данной статье рассмотрен один из разработанных макетов высокоточного комплекса средств измерений длины и приращений координат. Макет представляет собой высокоточный лазерный фазовый дальномер с доработанной системой приема и обработки измерительных сигналов. С помощью данного макета дальномера предлагается исследовать пути уменьшения составляющих его погрешности с целью повышения точности измерений длины. Для обеспечения наименьшей погрешности определения аппаратурной поправки макета дальномера могут служить средства из состава Государственного первичного специального эталона единицы длины. В качестве перспективных путей уменьшения погрешности определения разности фаз сигналов представляется возможным использовать устройства цифровой регистрации и обработки сигналов, в которых реализован метод расчета разности фаз сигналов путем математической обработки зарегистрированных данных с помощью специально разработанного вычислительного алгоритма на основе Фурье-анализа. Наиболее точное определение значений частоты следования импульсных сигналов и значений скорости света на измеряемой трассе может быть получено благодаря использованию высокоточных средств определения данных показателей. Реализация предложенных авторами методов повышения точности измерений длины лазерных фазовых дальномеров позволяет обеспечивать необходимый запас метрологической точности

On the Strength of Glasses

The remarkable strength of glasses is examined using the random first order transition theory of the glass transition. The theory predicts that strength depends on elastic modulus but also on the configurational energy frozen in when the glass is prepared. The stress catalysis of cooperative rearrangements of the type responsible for the supercooled liquid's high viscosity account quantitatively for the measured strength of a range of metallic glasses, silica and a polymer glass.Comment: 22 pages, 6 figure

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