Structure, dynamics and thermodynamics of single-file water under confinement: effects of polarizability of water molecules

Various structural, dynamic and thermodynamic properties of water molecules confined in single-wall carbon nanotubes (CNTs) are investigated using both polarizable and non-polarizable water models. The inclusion of polarizability quantitatively affects the nature of hydrogen bonding, which governs many properties of confined water molecules. Polarizable water leads to tighter hydrogen bonding and makes the distance between neighboring water molecules shorter than that for non-polarizable water. Stronger hydrogen bonding also decreases the rotational entropy and makes the diffusion constant smaller than in TIP3P and TIP3PM water models. The reorientational dynamics of the water molecules is governed by a jump mechanism, the barrier for the jump being highest for the polarizable water model. Our results highlight the role of polarizability in governing the dynamics of confined water and demonstrate that the inclusion of polarizability is necessary to obtain agreement with the results of ab initio simulations for the distributions of waiting and jump times. The SPC/E water model is found to predict various water properties in close agreement with the results of polarizable water models with much lower computational costs.

Oxygen potentials and phase equilibria in the system Ca-Co-O and thermodynamic properties of Ca3Co2O6 and Ca3Co4O9.163

Oxygen potentials established by the equilibrium between three condensed phases, CaOss+CoOss+ Ca3Co2O6 and CoOss+Ca3Co2O6+Ca3CO3.93+O-alpha(9.36-delta), are measured as a function of temperature using solid-state electrochemical cells incorporating yttria-stabilized zirconia as the electrolyte and pure oxygen as the reference electrode. Cation non-stoichiometry and oxygen non-stoichiometry in Ca3Co3.93+alpha O9.36-delta are determined using different techniques under defined conditions. Decomposition temperatures and thermodynamic properties of Ca3Co2O6 and Ca3Co4O9.163 are calculated from the results. The standard entropy and enthalpy of formation of Ca3Co2O6 at 298.15 K are evaluated. Using thermodynamic data from this study and auxiliary information from the literature, phase diagram for the ternary system Ca-Co-O is computed. Isothermal sections at representative temperatures are displayed to demonstrate the evolution of phase relations with temperature. (C) 2014 Elsevier Inc. All rights reserved.

A strongly coupled anisotropic fluid from dilaton driven holography

We consider a system consisting of 5 dimensional gravity with a negative cosmological constant coupled to a massless scalar, the dilaton. We construct a black brane solution which arises when the dilaton satisfies linearly varying boundary conditions in the asymptotically AdS(5) region. The geometry of this black brane breaks rotational symmetry while preserving translational invariance and corresponds to an anisotropic phase of the system. Close to extremality, where the anisotropy is big compared to the temperature, some components of the viscosity tensor become parametrically small compared to the entropy density. We study the quasi normal modes in considerable detail and find no instability close to extremality. We also obtain the equations for fluid mechanics for an anisotropic driven system in general, working upto first order in the derivative expansion for the stress tensor, and identify additional transport coefficients which appear in the constitutive relation. For the fluid of interest we find that the parametrically small viscosity can result in a very small force of friction, when the fluid is enclosed between appropriately oriented parallel plates moving with a relative velocity.

Monitoring urbanization and its implications in a mega city from space: Spatiotemporal patterns and its indicators

Rapid and invasive urbanization has been associated with depletion of natural resources (vegetation and water resources), which in turn deteriorates the landscape structure and conditions in the local environment. Rapid increase in population due to the migration from rural areas is one of the critical issues of the urban growth. Urbanisation in India is drastically changing the land cover and often resulting in the sprawl. The sprawl regions often lack basic amenities such as treated water supply, sanitation, etc. This necessitates regular monitoring and understanding of the rate of urban development in order to ensure the sustenance of natural resources. Urban sprawl is the extent of urbanization which leads to the development of urban forms with the destruction of ecology and natural landforms. The rate of change of land use and extent of urban sprawl can be efficiently visualized and modelled with the help of geo-informatics. The knowledge of urban area, especially the growth magnitude, shape geometry, and spatial pattern is essential to understand the growth and characteristics of urbanization process. Urban pattern, shape and growth can be quantified using spatial metrics. This communication quantifies the urbanisation and associated growth pattern in Delhi. Spatial data of four decades were analysed to understand land over and land use dynamics. Further the region was divided into 4 zones and into circles of 1 km incrementing radius to understand and quantify the local spatial changes. Results of the landscape metrics indicate that the urban center was highly aggregated and the outskirts and the buffer regions were in the verge of aggregating urban patches. Shannon's Entropy index clearly depicted the outgrowth of sprawl areas in different zones of Delhi. (C) 2014 Elsevier Ltd. All rights reserved.

Fragility correlates thermodynamic and kinetic properties of glass forming liquids

In our earlier communication we proposed a simple fragility determining function, (NBO]/(VmTg)-T-3), which we have now used to analyze several glass systems using available thermal data. A comparison with similar fragility determining function, Delta C-p/C-p(1), introduced by Chryssikos et al. in their investigation of lithium borate glasses has also been performed and found to be more convenient quantity for discussing fragilities. We now propose a new function which uses both Delta C-p and Delta T and which gives a numerical fragility parameter, F whose value lies between 0 and 1 for glass forming liquids. F can be calculated through the use of measured thermal parameters Delta C-p, C-p(1), T-g and T-m. Use of the new fragility values in reduced viscosity equation reproduces the whole range of viscosity curves of the Angell plot. The reduced viscosity equation can be directly compared with the Adam-Gibbs viscosity equation and a heat capacity function can be formulated which reproduces satisfactorily the Delta C-p versus In(T-r) curves and hence the configurational entropy. (C) 2014 Elsevier Ltd. All rights reserved.

Fragility correlates thermodynamic and kinetic properties of glass forming liquids

In our earlier communication we proposed a simple fragility determining function, (NBO]/(VmTg)-T-3), which we have now used to analyze several glass systems using available thermal data. A comparison with similar fragility determining function, Delta C-p/C-p(1), introduced by Chryssikos et al. in their investigation of lithium borate glasses has also been performed and found to be more convenient quantity for discussing fragilities. We now propose a new function which uses both Delta C-p and Delta T and which gives a numerical fragility parameter, F whose value lies between 0 and 1 for glass forming liquids. F can be calculated through the use of measured thermal parameters Delta C-p, C-p(1), T-g and T-m. Use of the new fragility values in reduced viscosity equation reproduces the whole range of viscosity curves of the Angell plot. The reduced viscosity equation can be directly compared with the Adam-Gibbs viscosity equation and a heat capacity function can be formulated which reproduces satisfactorily the Delta C-p versus In(T-r) curves and hence the configurational entropy. (C) 2014 Elsevier Ltd. All rights reserved.

Influence of dynamic operating conditions on the performance of metal hydride based solid sorption cooling systems

The performance of metal hydride based solid sorption cooling systems depends on the driving pressure differential, and the rate of hydrogen transfer between coupled metal hydride beds during cooling and regeneration processes. Conventionally, the mid-plateau pressure difference obtained from `static' equilibrium PCT data are used for the thermodynamic analysis. It is well known that the processes are `dynamic' because the pressure and temperature, and hence the concentration of the hydride beds, are continuously changing. Keeping this in mind, the pair of La0.9Ce0.1Ni5 - LaNi4.7Al0.3 metal hydrides suitable for solid sorption cooling systems were characterised using both static and dynamic methods. It was found that the PCT characteristics, and the resulting enthalpy (Delta H) and entropy (Delta S) values, were significantly different for static and dynamic modes of measurements. In the present study, the solid sorption metal hydride cooling system is analysed taking in to account the actual variation in the pressure difference (Delta P) and the dynamic enthalpy values. Compared to `static' property based analysis, significant decrease in the driving potentials and transferrable amounts of hydrogen, leading to decrease in cooling capacity by 57.8% and coefficient of performance by 31.9% are observed when dynamic PCT data at the flow rate of 80 ml/min are considered. Copyright 2014 (C) Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

Thermally developing combined electroosmotic and pressure-driven flow of nanofluids in a microchannel under the effect of magnetic field

In the present study, the heat transfer characteristics of thermally developing magnetohydroclynamic flow of nanofluid through microchannel are delineated by following a semi analytical approach. The combined influences of pressure driven flow, electroosmotic transport and magnetic field is taken into account for the analysis of the complex microscale thermal transport processes. Solutions for the normalized temperature distributions and the Nusselt number variations, considering the simultaneous interplay of electrokinetic effects (electroosmosis), magnetic effects, Joule heating and viscous dissipation are obtained, for constant wall temperature condition. Particular attention is paid to assess the role of nanolluids in altering the transport phenomena, through variations in the effective nanoparticle volume fractions, as well as the aggregate structure of the particulate phases. It is observed that magnetohydrodynamic effect reduces advective transport of the liquid resulting in gradual reduction of heat transfer. Increase in nanoparticle volume fraction shows decrease in heat transfer. Similar effects are observed with increase in aggregate sizes of the nanoparticles. The effect of the nanofluids on system irreversibility is also studied through entropy generation analysis due to flow and heat transfer in the microchannel. Total entropy generation is found to be dominant at the thermally developing region of the microchannel, whereas it drops sharply at the thermally developed region. Presence of nanoparticles in the base fluid reduces the total entropy generation in the microchannel, thereby indicating decrease in thermodynamic irreversibility with increasing nanoparticle volume fraction. (C) 2014 Elsevier Ltd. All rights reserved.

Nonlinear constraints on gravity from entanglement

Using the positivity of relative entropy arising from the Ryu-Takayanagi formula for spherical entangling surfaces, we obtain constraints at the nonlinear level for the gravitational dual. We calculate the Green's function necessary to compute the first order correction to the entangling surface and use this to find the relative entropy for non-constant stress tensors in a derivative expansion. We show that the Einstein value satisfies the positivity condition, while the multidimensional parameter space away from it gets constrained.

Low temperature giant magnetocaloric effect in multiferroic GdMnO3 single crystals

Magnetocaloric (MC) properties of GdMnO3 single crystals are investigated using magnetic and magneto-thermal measurements. GdMnO3 exhibits a giant MC effect (isothermal change in magnetic entropy (-Delta S-M) similar to 31 J (kg K)(-1) at 7 K and adiabatic change in temperature similar to 10 K at 19 K for magnetic field variation 0-80 kOe). Complex interactions between 3d and 4f magnetic sublattices influence MC properties. The rare-earth antiferromagnetic ordering induces an inverse MC effect (positive Delta S-M) along `a' and `c' axes whereas it's not seen along the `b' axis, revealing complex anisotropic magnetic ordering. The antiferromagnetic ordering possibly changes to ferromagnetic ordering at higher fields.

Viscosity bound for anisotropic superfluids in higher derivative gravity

In the present paper, based on the principles of gauge/gravity duality we analytically compute the shear viscosity to entropy (eta/s) ratio corresponding to the super fluid phase in Einstein Gauss-Bonnet gravity. From our analysis we note that the ratio indeed receives a finite temperature correction below certain critical temperature (T < T-c). This proves the non universality of eta/s ratio in higher derivative theories of gravity. We also compute the upper bound for the Gauss-Bonnet coupling (lambda) corresponding to the symmetry broken phase and note that the upper bound on the coupling does not seem to change as long as we are close to the critical point of the phase diagram. However the corresponding lower bound of the eta/s ratio seems to get modified due to the finite temperature effects.

Energy Sharing for Multiple Sensor Nodes With Finite Buffers

We consider the problem of finding optimal energy sharing policies that maximize the network performance of a system comprising of multiple sensor nodes and a single energy harvesting (EH) source. Sensor nodes periodically sense the random field and generate data, which is stored in the corresponding data queues. The EH source harnesses energy from ambient energy sources and the generated energy is stored in an energy buffer. Sensor nodes receive energy for data transmission from the EH source. The EH source has to efficiently share the stored energy among the nodes to minimize the long-run average delay in data transmission. We formulate the problem of energy sharing between the nodes in the framework of average cost infinite-horizon Markov decision processes (MDPs). We develop efficient energy sharing algorithms, namely Q-learning algorithm with exploration mechanisms based on the epsilon-greedy method as well as upper confidence bound (UCB). We extend these algorithms by incorporating state and action space aggregation to tackle state-action space explosion in the MDP. We also develop a cross entropy based method that incorporates policy parameterization to find near optimal energy sharing policies. Through simulations, we show that our algorithms yield energy sharing policies that outperform the heuristic greedy method.

Unusual Fragility and Cooperativity in Glass-Forming and Crystalline PVDF/PMMA Blends in the Presence of Multiwall Carbon Nanotubes

Poly(vinylidene fluoride) (PVDF) and poly(methyl methacrylate) (PMMA) are completely miscible below 50 wt % PVDF in the blends. In this work, an attempt was made to understand the fragility/cooperativity relation in glass-forming and crystalline blends of PVDF/PMMA and in the presence of a heteronucleating agent, multiwall carbon nanotubes (CNTs). Hence, three representative blends were chosen: a completely amorphous (10/90 by wt, PVDF/PMMA), on the verge of amorphous miscibility (50/50 by wt, PVDF/PMMA), and crystalline (60/40 by wt, PVDF/PMMA) blends. The intermolecular cooperativity/coupling, fragility, and configurational entropy near the glass transition temperature (T-g) were studied using differential scanning calorimetry (DSC) and broadband dielectric relaxation spectroscopy (DRS). It was observed that the blends with higher concentration of PMMA were more fragile (fragility index m = 141) and those with higher concentration of PVDF were more strong (m = 78). Interestingly, the coupling was less in the glass-forming blends (10/90 by wt, PVDF/PMMA) than the crystalline blends as manifested from DRS. This observation was also supported by DSC measurements which reflected that the cooperative rearranging region (CRR) existed over a smaller length scales in fragile blends as compared to strong blends, possibly due to restricted amorphous mobility. This effect was more prominent in the presence of CNTs, in particular for 50/50 (by wt) and 60/40 (by wt) PVDF/PMMA blends. Further, the configurational entropy, as manifested from DRS, decreased significantly in the strong blends in striking contrast to the fragile blends, supported by DSC, which manifested in an increase in the volume of cooperativity in the strong blends. The higher coupling in the crystalline blends can be attributed to good packing of the amorphous regions. While this is understood for crystalline blends (60/40 by wt, PVDF/PMMA), it is envisaged that enhanced dynamic heterogeneity is accountable for increased coupling in the case of blends which are on the verge of amorphous miscibility (50/50 by wt, PVDF/PMMA). The latter is also supported by broad relaxations near the T-g in DRS. Interestingly, the intermolecular coupling in the blends in the presence of CNTs has reduced, though the potential energy barrier hindering the rearrangement of CRR is lower than the blends without CNTs. In addition, the amorphous packing is not as effective as the blends without CNTs. This is manifested from reduced volume of cooperativity in particular, for 50/50 (by wt) and 60/40 (by wt) blends.

A Statistical Model of Current Loops and Magnetic Monopoles

We formulate a natural model of loops and isolated vertices for arbitrary planar graphs, which we call the monopole-dimer model. We show that the partition function of this model can be expressed as a determinant. We then extend the method of Kasteleyn and Temperley-Fisher to calculate the partition function exactly in the case of rectangular grids. This partition function turns out to be a square of a polynomial with positive integer coefficients when the grid lengths are even. Finally, we analyse this formula in the infinite volume limit and show that the local monopole density, free energy and entropy can be expressed in terms of well-known elliptic functions. Our technique is a novel determinantal formula for the partition function of a model of isolated vertices and loops for arbitrary graphs.

Non-Abelian gauge redundancy and entropic ambiguities

The von Neumann entropy of a generic quantum state is not unique unless the state can be uniquely decomposed as a sum of extremal or pure states. Therefore one reaches the remarkable possibility that there may be many entropies for a given state. We show that this happens if the GNS representation (of the algebra of observables in some quantum state) is reducible, and some representations in the decomposition occur with non-trivial degeneracy. This ambiguity in entropy, which can occur at zero temperature, can often be traced to a gauge symmetry emergent from the non-trivial topological character of the configuration space of the underlying system. We also establish the analogue of an H-theorem for this entropy by showing that its evolution is Markovian, determined by a stochastic matrix. After demonstrating this entropy ambiguity for the simple example of the algebra of 2 x 2 matrices, we argue that the degeneracies in the GNS representation can be interpreted as an emergent broken gauge symmetry, and play an important role in the analysis of emergent entropy due to non-Abelian anomalies. We work out the simplest situation with such non-Abelian symmetry, that of an ethylene molecule.