Information content of molecular graph and prediction of gas phase thermal entropy of organic compounds

Entropy is a fundamental thermodynamic property that has attracted a wide attention across domains, including chemistry. Inference of entropy of chemical compounds using various approaches has been a widely studied topic. However, many aspects of entropy in chemical compounds remain unexplained. In the present work, we propose two new information-theoretical molecular descriptors for the prediction of gas phase thermal entropy of organic compounds. The descriptors reflect the bulk and size of the compounds as well as the gross topological symmetry in their structures, all of which are believed to determine entropy. A high correlation () between the entropy values and our information-theoretical indices have been found and the predicted entropy values, obtained from the corresponding statistically significant regression model, have been found to be within acceptable approximation. We provide additional mathematical result in the form of a theorem and proof that might further help in assessing changes in gas phase thermal entropy values with the changes in molecular structures. The proposed information-theoretical molecular descriptors, regression model and the mathematical result are expected to augment predictions of gas phase thermal entropy for a large number of chemical compounds.

Entropy of quantum states: 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. As pointed out to us by Sorkin, 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 non-unique entropy can occur at zero temperature. We will argue elsewhere in detail 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. Finally, we establish the analogue of an H-theorem for this entropy by showing that its evolution is Markovian, determined by a stochastic matrix.

Frustration induced oscillator death on networks

An array of identical maps with Ising symmetry, with both positive and negative couplings, is studied. We divide the maps into two groups, with positive intra-group couplings and negative inter-group couplings. This leads to antisynchronization between the two groups which have the same stability properties as the synchronized state. Introducing a certain degree of randomness in signs of these couplings destabilizes the anti-synchronized state. Further increasing the randomness in signs of these couplings leads to oscillator death. This is essentially a frustration induced phenomenon. We explain the observed results using the theory of random matrices with nonzero mean. We briefly discuss applications to coupled differential equations. (C) 2013 AIP Publishing LLC.

New rock salt-related oxides Li3M2RuO6 (M=Co, Ni): Synthesis, structure, magnetism and electrochemistry

We describe the synthesis, crystal structure, magnetic and electrochemical characterization of new rock salt-related oxides of formula, Li3M2RuO6 (M=Co, Ni). The M=Co oxide adopts the LiCoO2 (R-3m) structure, where sheets of LiO6 and (Co-2/Ru)O-6 octahedra are alternately stacked along the c-direction. The M=Ni oxide also adopts a similar layered structure related to Li2TiO3, where partial mixing of Li and Ni/Ru atoms lowers the symmetry to monoclinic (C2/c). Magnetic susceptibility measurements reveal that in Li3Co2RuO6, the oxidation states of transition metal ions are Co3+ (S=0), Co2+ (S=1/2) and Ru4+ (S=1), all of them in low-spin configuration and at 10 K, the material orders antiferromagnetically. Analogous Li3Ni2RuO6 presents a ferrimagnetic behavior with a Curie temperature of 100 K. The differences in the magnetic behavior have been explained in terms of differences in the crystal structure. Electrochemical studies correlate well with both magnetic properties and crystal structure. Li-transition metal intermixing may be at the origin of the more impeded oxidation of Li3Ni2RuO6 when compared to Li3CO2RuO6. Interestingly high first charge capacities (between ca. 160 and 180 mAh g(-1)) corresponding to ca. 2/3 of theoretical capacity are reached albeit, in both cases, capacity retention and cyclability are not satisfactory enough to consider these materials as alternatives to LiCoO2. (C) 2013 Elsevier Inc. All rights reserved.

Regional variations in the nonlinearity and anisotropy of bovine aortic elastin

Arterial walls have a regular and lamellar organization of elastin present as concentric fenestrated networks in the media. In contrast, elastin networks are longitudinally oriented in layers adjacent to the media. In a previous model exploring the biomechanics of arterial elastin, we had proposed a microstructurally motivated strain energy function modeled using orthotropic material symmetry. Using mechanical experiments, we showed that the neo-Hookean term had a dominant contribution to the overall form of the strain energy function. In contrast, invariants corresponding to the two fiber families had smaller contributions. To extend these investigations, we use biaxial force-controlled experiments to quantify regional variations in the anisotropy and nonlinearity of elastin isolated from bovine aortic tissues proximal and distal to the heart. Results from this study show that tissue nonlinearity significantly increases distal to the heart as compared to proximally located regions (). Distally located samples also have a trend for increased anisotropy (), with the circumferential direction stiffer than the longitudinal, as compared to an isotropic and relatively linear response for proximally located elastin samples. These results are consistent with the underlying tissue histology from proximally located samples that had higher optical density (), fiber thickness (), and trend for lower tortuosity () in elastin fibers as compared to the thinner and highly undulating elastin fibers isolated from distally located samples. Our studies suggest that it is important to consider elastin fiber orientations in investigations that use microstructure-based models to describe the contributions of elastin and collagen to arterial mechanics.

Confinement induced stochastic sensing of charged coronene and perylene aggregates in alpha-hemolysin nanochannels

Biological nanopores provide optimum dimensions and an optimal environment to study early aggregation kinetics of charged polyaromatic molecules in the nano-confined regime. It is expected that probing early stages of nucleation will enable us to design a strategy for supramolecular assembly and biocrystallization processes. Specifically, we have studied translocation dynamics of coronene and perylene based salts, through the alpha-hemolysin (alpha-HL) protein nanopore. The characteristic blocking events in the time-series signal are a function of concentration and bias voltage. We argue that different blocking events arise due to different aggregation processes as captured by all atomistic molecular dynamics (MD) simulations. These confinement induced aggregations of polyaromatic chromophores during the different stages of translocation are correlated with the spatial symmetry and charge distribution of the molecules.

Learning from positive and unlabelled examples using maximum margin clustering

Learning from Positive and Unlabelled examples (LPU) has emerged as an important problem in data mining and information retrieval applications. Existing techniques are not ideally suited for real world scenarios where the datasets are linearly inseparable, as they either build linear classifiers or the non-linear classifiers fail to achieve the desired performance. In this work, we propose to extend maximum margin clustering ideas and present an iterative procedure to design a non-linear classifier for LPU. In particular, we build a least squares support vector classifier, suitable for handling this problem due to symmetry of its loss function. Further, we present techniques for appropriately initializing the labels of unlabelled examples and for enforcing the ratio of positive to negative examples while obtaining these labels. Experiments on real-world datasets demonstrate that the non-linear classifier designed using the proposed approach gives significantly better generalization performance than the existing relevant approaches for LPU.

Structure constants of beta deformed super Yang-Mills

We study the structure constants of the N = 1 beta deformed theory perturbatively and at strong coupling. We show that the planar one loop corrections to the structure constants of single trace gauge invariant operators in the scalar sector is determined by the anomalous dimension Hamiltonian. This result implies that 3 point functions of the chiral primaries of the theory do not receive corrections at one loop. We then study the structure constants at strong coupling using the Lunin-Maldacena geometry. We explicitly construct the supergravity mode dual to the chiral primary with three equal U(1) R-charges in the Lunin-Maldacena geometry. We show that the 3 point function of this supergravity mode with semi-classical states representing two other similar chiral primary states but with large U(1) charges to be independent of the beta deformation and identical to that found in the AdS(5) x S-5 geometry. This together with the one-loop result indicate that these structure constants are protected by a non-renormalization theorem. We also show that three point function of U(1) R-currents with classical massive strings is proportional to the R-charge carried by the string solution. This is in accordance with the prediction of the R-symmetry Ward identity.

Hard-core bosons in a zig-zag optical superlattice

We study a system of hard-core bosons at half-filling in a one-dimensional optical superlattice. The bosons are allowed to hop to nearest-and next-nearest-neighbor sites. We obtain the ground-state phase diagram as a function of microscopic parameters using the finite-size density-matrix renormalization-group method. Depending on the sign of the next-nearest-neighbor hopping and the strength of the superlattice potential the system exhibits three different phases, namely the bond-order (BO) solid, the superlattice induced Mott insulator (SLMI), and the superfluid (SF) phase. When the signs of both hopping amplitudes are the same (the unfrustratedase), the system undergoes a transition from the SF to the SLMI at a nonzero value of the superlattice potential. On the other hand, when the two amplitudes differ in sign (the frustrated case), the SF is unstable to switching on a superlattice potential and also exists only up to a finite value of the next-nearest-neighbor hopping. This part of the phase diagram is dominated by the BO phase which breaks translation symmetry spontaneously even in the absence of the superlattice potential and can thus be characterized by a bond-order parameter. The transition from BO to SLMI appears to be first order.

Low temperature combustion synthesis and magnetostructural properties of Co-Mn nanoferrites

In the present work, Co1-xMnxFe2O4 nanoparticles were synthesized by the low-temperature auto-combustion method. The thermal decomposition process was investigated by means of differential and thermal gravimetric analysis (TG-DTA) that showed the precursor yield the final product above 450 degrees C. The phase purity and crystal lattice symmetry were estimated from X-ray diffraction (XRD). Microstructural features observed by scanning electron microscopy (SEM) demonstrates that the fine clustered particles were formed with an increase in average grain size with Mn2+ content. Fourier transform infrared spectroscopy (FTIR) study confirms the formation of spinel ferrite. Room temperature magnetization measurements showed that the magnetization M-s increases from 29 to 60 emu/g and H-c increases from 13 to 28 Oe with increase in Mn2+ content, which implies that these materials may be applicable for magnetic data storage and recording media. (C) 2013 Elsevier B.V. All rights reserved.

Effects of initial height on the steady-state persistence probability of linear growth models

The effects of the initial height on the temporal persistence probability of steady-state height fluctuations in up-down symmetric linear models of surface growth are investigated. We study the (1 + 1)-dimensional Family model and the (1 + 1)-and (2 + 1)-dimensional larger curvature (LC) model. Both the Family and LC models have up-down symmetry, so the positive and negative persistence probabilities in the steady state, averaged over all values of the initial height h(0), are equal to each other. However, these two probabilities are not equal if one considers a fixed nonzero value of h(0). Plots of the positive persistence probability for negative initial height versus time exhibit power-law behavior if the magnitude of the initial height is larger than the interface width at saturation. By symmetry, the negative persistence probability for positive initial height also exhibits the same behavior. The persistence exponent that describes this power-law decay decreases as the magnitude of the initial height is increased. The dependence of the persistence probability on the initial height, the system size, and the discrete sampling time is found to exhibit scaling behavior.

Quantum Phase Diagram of One-Dimensional Spin and Hubbard Models with Transitions to Bond Order Wave Phases

Similar quantum phase diagrams and transitions are found for three classes of one-dimensional models with equally spaced sites, singlet ground states (GS), inversion symmetry at sites and a bond order wave (BOW) phase in some sectors. The models are frustrated spin-1/2 chains with variable range exchange, half-filled Hubbard models with spin-independent interactions and modified Hubbard models with site energies for describing organic charge transfer salts. In some range of parameters, the models have a first order quantum transition at which the GS expectation value of the sublattice spin < S-A(2)> of odd or even-numbered sites is discontinuous. There is an intermediate BOW phase for other model parameters that lead to two continuous quantum transitions with continuous < S-A(2)>. Exact diagonalization of finite systems and symmetry arguments provide a unified picture of familiar 1D models that have appeared separately in widely different contexts.

Quantum Phase Diagram of One-Dimensional Spin and Hubbard Models with Transitions to Bond Order Wave Phases

Similar quantum phase diagrams and transitions are found for three classes of one-dimensional models with equally spaced sites, singlet ground states (GS), inversion symmetry at sites and a bond order wave (BOW) phase in some sectors. The models are frustrated spin-1/2 chains with variable range exchange, half-filled Hubbard models with spin-independent interactions and modified Hubbard models with site energies for describing organic charge transfer salts. In some range of parameters, the models have a first order quantum transition at which the GS expectation value of the sublattice spin < S-A(2)> of odd or even-numbered sites is discontinuous. There is an intermediate BOW phase for other model parameters that lead to two continuous quantum transitions with continuous < S-A(2)>. Exact diagonalization of finite systems and symmetry arguments provide a unified picture of familiar 1D models that have appeared separately in widely different contexts.

Compact in-plane dual-axis spring-steel accelerometer

Presented in this paper is an improvement over a spring-steel dual-axis accelerometer that we had reported earlier.The fabrication process (which entails wire-cut electro discharge machining of easily accessible and inexpensive spring-steelfoil) and the sensing of the displacement (which is done using off-the-shelf Hall-effect sensors) remain the same. Theimprovements reported here are twofold: (i) the footprint of the packaged accelerometer is reduced from 80 mm square to 40mm square, and (ii) almost perfect de-coupling and symmetry are achieved between the two in-plane axes of the packageddevice as opposed to the previous embodiment where this was not the case. Good linearity with about 40 mV/g was measuredalong both the in-plane axes over a range of 0.1 to 1 g. The first two natural frequencies of the devices are at 30 Hz and 100Hz, respectively, as per the experiment. The highlights of this work are cost-effective processing, easy integration of the Hall-effect sensing capability on a customised printed circuit board, and inexpensive packaging without overly compromising eitherthe overall size or the sensitivity of the accelerometer. Through this work, we have reaffirmed the practicability of spring-steelaccelerometers towards the eventual goal of making it compete with micro machined silicon accelerometers in terms of sizeand performance. The cost is likely to be much lower for the spring-steel accelerometers than that of silicon accelerometers, especially when the volume of production is low and the sensor is to be used as a single packaged unit.

Universal Conductance Fluctuations as a direct probe to valley coherence and universality class of disordered graphene

We demonstrate that the universal conductance fluctuations (UCF) can be used as a direct probe to study the valley quantum states in disordered graphene. The UCF magnitude in graphene is suppressed by a factor of four at high carrier densities where the short-range disorder essentially breaks the valley degeneracy of the K and K' valleys, leading to a density dependent crossover of symmetry class from symplectic near the Dirac point to orthogonal at high densities.