Adam-Gibbs Relation for Glass-Forming Liquids in Two, Three, and Four Dimensions

The Adam-Gibbs relation between relaxation times and the configurational entropy has been tested extensively for glass formers using experimental data and computer simulation results. Although the form of the relation contains no dependence on the spatial dimensionality in the original formulation, subsequent derivations of the Adam-Gibbs relation allow for such a possibility. We test the Adam-Gibbs relation in two, three, and four spatial dimensions using computer simulations of model glass formers. We find that the relation is valid in three and four dimensions. But in two dimensions, the relation does not hold, and interestingly, no single alternate relation describes the results for the different model systems we study.

Molecular probe dynamics reveals suppression of ice-like regions in strongly confined supercooled water

The structure of the hydrogen bond network is a key element for understanding water's thermodynamic and kinetic anomalies. While ambient water is strongly believed to be a uniform, continuous hydrogen-bonded liquid, there is growing consensus that supercooled water is better described in terms of distinct domains with either a low-density ice-like structure or a high-density disordered one. We evidenced two distinct rotational mobilities of probe molecules in interstitial supercooled water of polycrystalline ice Banerjee D, et al. (2009) ESR evidence for 2 coexisting liquid phases in deeply supercooled bulk water. Proc Natl Acad Sci USA 106: 11448-11453]. Here we show that, by increasing the confinement of interstitial water, the mobility of probe molecules, surprisingly, increases. We argue that loose confinement allows the presence of ice-like regions in supercooled water, whereas a tighter confinement yields the suppression of this ordered fraction and leads to higher fluidity. Compelling evidence of the presence of ice-like regions is provided by the probe orientational entropy barrier which is set, through hydrogen bonding, by the configuration of the surrounding water molecules and yields a direct measure of the configurational entropy of the same. We find that, under loose confinement of supercooled water, the entropy barrier surmounted by the slower probe fraction exceeds that of equilibrium water by the melting entropy of ice, whereas no increase of the barrier is observed under stronger confinement. The lower limit of metastability of supercooled water is discussed.

Magnetocaloric effect and nature of magnetic transition in nanoscale Pr0.5Ca0.5MnO3

Systematic measurements pertinent to the magnetocaloric effect and nature of magnetic transition around the transition temperature are performed in the 10 nm Pr0.5Ca0.5MnO3 nanoparticles (PCMO10). Maxwell's relation is employed to estimate the change in magnetic entropy. At Curie temperature (T-C) similar to 83.5 K, the change in magnetic entropy (-Delta S-M) discloses a typical variation with a value 0.57 J/kg K, and is found to be magnetic field dependent. From the area under the curve (Delta S vs T), the refrigeration capacity is calculated at T-C similar to 83.5K and it is found to be 7.01 J/kg. Arrott plots infer that due to the competition between the ferromagnetic and anti-ferromagnetic interactions, the magnetic phase transition in PCMO10 is broadly spread over both in temperature as well as magnetic field coordinates. Upon tuning the particle size, size distribution, morphology, and relative fraction of magnetic phases, it may be possible to enhance the magnetocalorific effect further in PCMO10. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.4759372]

Thermodynamics of TmRhO3, Phase Equilibria, and Chemical Potentials in the System Tm-Rh-O

Phase equilibria in the system Tm-Rh-O at 1200 K is established by isothermal equilibration of selected compositions and phase identification after quenching to room temperature. Six intermetallic phases (Tm3Rh, Tm7Rh3, Tm5Rh3, Tm3Rh2, TmRh, TmRh2 +/-delta) and a ternary oxide TmRhO3 are identified. Based on experimentally determined phase relations, a solid-state electrochemical cell is devised to measure the standard free energy of formation of orthorhombic perovskite TmRhO3 from cubic Tm2O3 and beta-Rh2O3 in the temperature range from (900 to 1300) K. The results can be summarized as: Delta G(f,ox)(o) +/- 104/J.mol(-1) = -46474 + 3.925(T/K). Invoking the Neumann-Kopp rule, the standard enthalpy of formation of TmRhO3 from its constituent elements at 298.15 K is estimated as -1193.89 (+/- 2.86) kJ.mol(-1). The standard entropy of TmRhO3 at 298.15 K is evaluated as 103.8 (+/- 1.6) J.mol(-1).K-1. The oxygen potential-composition diagram and three-dimensional chemical potential diagram at 1200 K and temperature-composition diagrams at constant partial pressures of oxygen are computed from thermodynamic data. The compound TmRhO3 decomposes at 1688 (+/- 2) K in pure oxygen and at 1583 (+/- 2) K in air at standard pressure.

Simulation of Influence of Bilayer Melting on Dynamics and Thermodynamics of Interfacial Water

We investigate the effect of bilayer melting transition on thermodynamics and dynamics of interfacial water using molecular dynamics simulation with the two-phase thermodynamic model. We show that the diffusivity of interface water depicts a dynamic crossover at the chain melting transition following an Arrhenius behavior until the transition temperature. The corresponding change in the diffusion coefficient from the bulk to the interface water is comparable with experimental observations found recently for water near 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) vesicles Phys. Chem. Chem. Phys. 13, 7732 (2011)]. The entropy and potential energy of interfacial water show distinct changes at the bilayer melting transition, indicating a strong correlation in the thermodynamic state of water and the accompanying first-order phase transition of the bilayer membrane. DOI: 10.1103/PhysRevLett.110.018303

q-Gaussian based Smoothed Functional Algorithms for Stochastic Optimization

The q-Gaussian distribution results from maximizing certain generalizations of Shannon entropy under some constraints. The importance of q-Gaussian distributions stems from the fact that they exhibit power-law behavior, and also generalize Gaussian distributions. In this paper, we propose a Smoothed Functional (SF) scheme for gradient estimation using q-Gaussian distribution, and also propose an algorithm for optimization based on the above scheme. Convergence results of the algorithm are presented. Performance of the proposed algorithm is shown by simulation results on a queuing model.

Diversity in ranking via resistive graph centers

Users can rarely reveal their information need in full detail to a search engine within 1--2 words, so search engines need to "hedge their bets" and present diverse results within the precious 10 response slots. Diversity in ranking is of much recent interest. Most existing solutions estimate the marginal utility of an item given a set of items already in the response, and then use variants of greedy set cover. Others design graphs with the items as nodes and choose diverse items based on visit rates (PageRank). Here we introduce a radically new and natural formulation of diversity as finding centers in resistive graphs. Unlike in PageRank, we do not specify the edge resistances (equivalently, conductances) and ask for node visit rates. Instead, we look for a sparse set of center nodes so that the effective conductance from the center to the rest of the graph has maximum entropy. We give a cogent semantic justification for turning PageRank thus on its head. In marked deviation from prior work, our edge resistances are learnt from training data. Inference and learning are NP-hard, but we give practical solutions. In extensive experiments with subtopic retrieval, social network search, and document summarization, our approach convincingly surpasses recently-published diversity algorithms like subtopic cover, max-marginal relevance (MMR), Grasshopper, DivRank, and SVMdiv.

Extended histories: improving regularity and performance in correlation prefetchers

Data Prefetchers identify and make use of any regularity present in the history/training stream to predict future references and prefetch them into the cache. The training information used is typically the primary misses seen at a particular cache level, which is a filtered version of the accesses seen by the cache. In this work we demonstrate that extending the training information to include secondary misses and hits along with primary misses helps improve the performance of prefetchers. In addition to empirical evaluation, we use the information theoretic metric entropy, to quantify the regularity present in extended histories. Entropy measurements indicate that extended histories are more regular than the default primary miss only training stream. Entropy measurements also help corroborate our empirical findings. With extended histories, further benefits can be achieved by triggering prefetches during secondary misses also. In this paper we explore the design space of extended prefetch histories and alternative prefetch trigger points for delta correlation prefetchers. We observe that different prefetch schemes benefit to a different extent with extended histories and alternative trigger points. Also the best performing design point varies on a per-benchmark basis. To meet these requirements, we propose a simple adaptive scheme that identifies the best performing design point for a benchmark-prefetcher combination at runtime. In SPEC2000 benchmarks, using all the L2 accesses as history for prefetcher improves the performance in terms of both IPC and misses reduced over techniques that use only primary misses as history. The adaptive scheme improves the performance of CZone prefetcher over Baseline by 4.6% on an average. These performance gains are accompanied by a moderate reduction in the memory traffic requirements.

A nested linear codes approach to distributed function computation over subspaces

In this paper, we consider a distributed function computation setting, where there are m distributed but correlated sources X1,...,Xm and a receiver interested in computing an s-dimensional subspace generated by [X1,...,Xm]Γ for some (m × s) matrix Γ of rank s. We construct a scheme based on nested linear codes and characterize the achievable rates obtained using the scheme. The proposed nested-linear-code approach performs at least as well as the Slepian-Wolf scheme in terms of sum-rate performance for all subspaces and source distributions. In addition, for a large class of distributions and subspaces, the scheme improves upon the Slepian-Wolf approach. The nested-linear-code scheme may be viewed as uniting under a common framework, both the Korner-Marton approach of using a common linear encoder as well as the Slepian-Wolf approach of employing different encoders at each source. Along the way, we prove an interesting and fundamental structural result on the nature of subspaces of an m-dimensional vector space V with respect to a normalized measure of entropy. Here, each element in V corresponds to a distinct linear combination of a set {Xi}im=1 of m random variables whose joint probability distribution function is given.

Further results on geometric properties of a family of relative entropies

This paper extends some geometric properties of a one-parameter family of relative entropies. These arise as redundancies when cumulants of compressed lengths are considered instead of expected compressed lengths. These parametric relative entropies are a generalization of the Kullback-Leibler divergence. They satisfy the Pythagorean property and behave like squared distances. This property, which was known for finite alphabet spaces, is now extended for general measure spaces. Existence of projections onto convex and certain closed sets is also established. Our results may have applications in the Rényi entropy maximization rule of statistical physics.

QUAD: quality assessment of documents

We propose a set of metrics that evaluate the uniformity, sharpness, continuity, noise, stroke width variance,pulse width ratio, transient pixels density, entropy and variance of components to quantify the quality of a document image. The measures are intended to be used in any optical character recognition (OCR) engine to a priori estimate the expected performance of the OCR. The suggested measures have been evaluated on many document images, which have different scripts. The quality of a document image is manually annotated by users to create a ground truth. The idea is to correlate the values of the measures with the user annotated data. If the measure calculated matches the annotated description,then the metric is accepted; else it is rejected. In the set of metrics proposed, some of them are accepted and the rest are rejected. We have defined metrics that are easily estimatable. The metrics proposed in this paper are based on the feedback of homely grown OCR engines for Indic (Tamil and Kannada) languages. The metrics are independent of the scripts, and depend only on the quality and age of the paper and the printing. Experiments and results for each proposed metric are discussed. Actual recognition of the printed text is not performed to evaluate the proposed metrics. Sometimes, a document image containing broken characters results in good document image as per the evaluated metrics, which is part of the unsolved challenges. The proposed measures work on gray scale document images and fail to provide reliable information on binarized document image.

Evaluation of isopentane, R-245fa and their mixtures as working fluids for organic Rankine cycles

Low grade thermal energy from sources such as solar, geothermal and industrial waste heat in the temperature range of 380-425 K can be converted to electrical energy with reasonable efficiency using isopentane and R-245fa. While the former is flammable and the latter has considerable global warming potential, their mixture in 0.7/0.3 mole fraction is shown to obviate these disadvantages and yet retain dominant merits of each fluid. A realistic thermodynamic analysis is carried out wherein the possible sources of irreversibilities such as isentropic efficiencies of the expander and the pump and entropy generation in the regenerator, boiler and condenser are accounted for. The performance of the system in the chosen range of heat source temperatures is evaluated. A technique of identifying the required source temperature for a given output of the plant and the maximum operating temperature of the working fluid is developed. This is based on the pinch point occurrence in the boiler and entropy generation in the boiling and superheating regions of the boiler. It is shown that cycle efficiencies of 10-13% can be obtained in the range investigated at an optimal expansion ratio of 7-10. (C) 2012 Elsevier Ltd. All rights reserved.

Linear Coding Schemes for the Distributed Computation of Subspaces

Let X-1,..., X-m be a set of m statistically dependent sources over the common alphabet F-q, that are linearly independent when considered as functions over the sample space. We consider a distributed function computation setting in which the receiver is interested in the lossless computation of the elements of an s-dimensional subspace W spanned by the elements of the row vector X-1,..., X-m]Gamma in which the (m x s) matrix Gamma has rank s. A sequence of three increasingly refined approaches is presented, all based on linear encoders. The first approach uses a common matrix to encode all the sources and a Korner-Marton like receiver to directly compute W. The second improves upon the first by showing that it is often more efficient to compute a carefully chosen superspace U of W. The superspace is identified by showing that the joint distribution of the {X-i} induces a unique decomposition of the set of all linear combinations of the {X-i}, into a chain of subspaces identified by a normalized measure of entropy. This subspace chain also suggests a third approach, one that employs nested codes. For any joint distribution of the {X-i} and any W, the sum-rate of the nested code approach is no larger than that under the Slepian-Wolf (SW) approach. Under the SW approach, W is computed by first recovering each of the {X-i}. For a large class of joint distributions and subspaces W, the nested code approach is shown to improve upon SW. Additionally, a class of source distributions and subspaces are identified, for which the nested-code approach is sum-rate optimal.

Evaluation of carbon dioxide blends with isopentane and propane as working fluids for organic Rankine cycles

The main theme of this paper is to study the flammability suppression of hydrocarbons by blending with carbon dioxide, and to evaluate these mixtures as possible working fluids in organic Rankine cycle for medium temperature concentrated solar power applications. The analysis takes into account inevitable irreversibilities in the turbine, the pump, and heat exchangers. While the isopentane + CO2 mixture suffers from high irreversibility mainly in the regenerator owing to a large temperature glide, the propane + CO2 mixture performs more or less the same as pure propane albeit with high cycle pressures. In general, large temperature glides at condensing pressures extend the heat recovery into the two-phase dome, which is an advantage. However, at the same time, the shift of the pinch point towards the warm end of the regenerator is found to be a major cause of irreversibility. In fact, as the number of carbon atoms in alkanes decreases, their blend with CO2 moves the pinch point to the colder end of the regenerator. This results in lower entropy generation in the regenerator and improved cycle efficiency of propane + CO2 mixtures. With this mixture, real cycle efficiencies of 15-18% are achievable at a moderate source temperature of 573 K. Applicability for a wide range of source temperatures is found to be an added advantage of this mixture.

Can the viscosity in astrophysical black hole accretion disks be close to its string theory bound?

String theory and gauge/gravity duality suggest the lower bound of shear viscosity (eta) to entropy density (s) for any matter to be mu h/4 pi k(B), when h and k(B) are reduced Planck and Boltzmann constants respectively and mu <= 1. Motivated by this, we explore eta/s in black hole accretion flows, in order to understand if such exotic flows could be a natural site for the lowest eta/s. Accretion flow plays an important role in black hole physics in identifying the existence of the underlying black hole. This is a rotating shear flow with insignificant molecular viscosity, which could however have a significant turbulent viscosity, generating transport, heat and hence entropy in the flow. However, in presence of strong magnetic field, magnetic stresses can help in transporting matter independent of viscosity, via celebrated Blandford-Payne mechanism. In such cases, energy and then entropy produces via Ohmic dissipation. In,addition, certain optically thin, hot, accretion flows, of temperature greater than or similar to 10(9) K, may be favourable for nuclear burning which could generate/absorb huge energy, much higher than that in a star. We find that eta/s in accretion flows appears to be close to the lower bound suggested by theory, if they are embedded by strong magnetic field or producing nuclear energy, when the source of energy is not viscous effects. A lower bound on eta/s also leads to an upper bound on the Reynolds number of the flow.