A note on the evaluation of dielectric dispersion parameters of non-debije type liquids

A simple method for evaluating dielectric relaxation parameters ie given whioh can be used for analyeing the arelaxation times of a liquid into two absorptions.

The problem of liquid droplet combustion-reexamination

The simple quasi-steady analysis of the combustion of a liquid fuel droplet in an oxidising atmosphere provides unsatisfactory explanations for several experimental observations. It's prediction of values for the burning constant (K), the flame-to-droplet diameter ratio ( ) and the flame temperature (Tf) have been found to be amgibuous if not completely inaccurate. A critical survey of the literature has led us to a detailed examination of the effects of unsteadiness and variable properties. The work published to date indicates that the gas-phase unsteadiness is relatively short and therefore quite insignificant.A new theoretical analysis based on heat transfer within the droplet is presented here. It shows that the condensed-phase unsteadiness lasts for about 20â??25% of the total burning time. It is concluded that the discrepancies between experimental observations and the predictions of the constant-property quasi-steady analysis cannot be attributed either to gas-phase or condensed-phase unsteadiness.An analytical model of quasi-steady droplet combustion with variable thermodynamic and transport properties and non-unity Lewis numbers will be examined. Further findings reveal a significant improvement in the prediction of combustion parameters, particularly of K, when consideration is given to variations of cp and λ with the temperature and concentrations of several species. Tf is accurately predicted when the required conditions of incomplete combustion or low ( ) at the flame are met. Further refinement through realistic Lewis numbers predicts ( ) meaningfully.

Vitrification, relaxation and free volume in glycerol-water binary liquid mixture:Spin probe ESR studies

Glass transition and relaxation of the glycerol-water (G-W) binary mixture system have been studied over the glycerol concentration range of 5-85 mol% by using the highly sensitive technique of electron spin resonance (ESR). For the water rich mixture the glass transition,sensed by the dissolved spin probe, arises from the vitrified mesoscopic portion of the binary system. The concentration dependence of the glass transition temperature manifests a closely related molecular level cooperativity in the system. A drastic change in the mesoscopic structure of the system at the critical concentration of 40 mol is confirmed by an estimation of the spin probe effective volume in a temperature range where the tracer reorientation is strongly coupled to the system dynamics.

Low-delay, high-rate, non-square STBCs from scaled complex orthogonal designs

Space-time block codes (STBCs) obtained from non-square complex orthogonal designs are bandwidth efficient compared to those from square real/complex orthogonal designs for colocated coherent MIMO systems and has other applications in (i) non-coherent MIMO systems with non-differential detection, (ii) Space-Time-Frequency codes for MIMO-OFDM systems and (iii) distributed space-time coding for relay channels. Liang (IEEE Trans. Inform. Theory, 2003) has constructed maximal rate non-square designs for any number of antennas, with rates given by [(a+1)/(2a)] when number of transmit antennas is 2a-1 or 2a. However, these designs have large delays. When large number of antennas are considered this rate is close to 1/2. Tarokh et al (IEEE Trans. Inform. Theory, 1999) have constructed rate 1/2 non-square CODs using the rate-1 real orthogonal designs for any number of antennas, where the decoding delay of these codes is less compared to the codes constructed by Liang for number of transmit antennas more than 5. In this paper, we construct a class of rate-1/2 codes for arbitrary number of antennas where the decoding delay is reduced by 50% when compared with the rate-1/2 codes given by Tarokh et al. It is also shown that even though scaling the variables helps to lower the delay it can not be used to increase the rate.

Novel fluorescence detection technique for non-contact temperature sensing in microchip PCR

DNA amplification using Polymerase Chain Reaction (PCR) in a small volume is used in Lab-on-a-chip systems involving DNA manipulation. For few microliters of volume of liquid, it becomes difficult to measure and monitor the thermal profile accurately and reproducibly, which is an essential requirement for successful amplification. Conventional temperature sensors are either not biocompatible or too large and hence positioned away from the liquid leading to calibration errors. In this work we present a fluorescence based detection technique that is completely biocompatible and measures directly the liquid temperature. PCR is demonstrated in a 3 ILL silicon-glass microfabricated device using non-contact induction heating whose temperature is controlled using fluorescence feedback from SYBR green I dye molecules intercalated within sensor DNA. The performance is compared with temperature feedback using a thermocouple sensor. Melting curve followed by gel electrophoresis is used to confirm product specificity after the PCR cycles. (c) 2007 Elsevier B.V. All rights reserved.

Monte Carlo Simulations of Molecular Clusters in Nucleation

A better understanding of the limiting step in a first order phase transition, the nucleation process, is of major importance to a variety of scientific fields ranging from atmospheric sciences to nanotechnology and even to cosmology. This is due to the fact that in most phase transitions the new phase is separated from the mother phase by a free energy barrier. This barrier is crossed in a process called nucleation. Nowadays it is considered that a significant fraction of all atmospheric particles is produced by vapor-to liquid nucleation. In atmospheric sciences, as well as in other scientific fields, the theoretical treatment of nucleation is mostly based on a theory known as the Classical Nucleation Theory. However, the Classical Nucleation Theory is known to have only a limited success in predicting the rate at which vapor-to-liquid nucleation takes place at given conditions. This thesis studies the unary homogeneous vapor-to-liquid nucleation from a statistical mechanics viewpoint. We apply Monte Carlo simulations of molecular clusters to calculate the free energy barrier separating the vapor and liquid phases and compare our results against the laboratory measurements and Classical Nucleation Theory predictions. According to our results, the work of adding a monomer to a cluster in equilibrium vapour is accurately described by the liquid drop model applied by the Classical Nucleation Theory, once the clusters are larger than some threshold size. The threshold cluster sizes contain only a few or some tens of molecules depending on the interaction potential and temperature. However, the error made in modeling the smallest of clusters as liquid drops results in an erroneous absolute value for the cluster work of formation throughout the size range, as predicted by the McGraw-Laaksonen scaling law. By calculating correction factors to Classical Nucleation Theory predictions for the nucleation barriers of argon and water, we show that the corrected predictions produce nucleation rates that are in good comparison with experiments. For the smallest clusters, the deviation between the simulation results and the liquid drop values are accurately modelled by the low order virial coefficients at modest temperatures and vapour densities, or in other words, in the validity range of the non-interacting cluster theory by Frenkel, Band and Bilj. Our results do not indicate a need for a size dependent replacement free energy correction. The results also indicate that Classical Nucleation Theory predicts the size of the critical cluster correctly. We also presents a new method for the calculation of the equilibrium vapour density, surface tension size dependence and planar surface tension directly from cluster simulations. We also show how the size dependence of the cluster surface tension in equimolar surface is a function of virial coefficients, a result confirmed by our cluster simulations.

Monte Carlo simulations of molecular clusters in nucleation

A better understanding of the limiting step in a first order phase transition, the nucleation process, is of major importance to a variety of scientific fields ranging from atmospheric sciences to nanotechnology and even to cosmology. This is due to the fact that in most phase transitions the new phase is separated from the mother phase by a free energy barrier. This barrier is crossed in a process called nucleation. Nowadays it is considered that a significant fraction of all atmospheric particles is produced by vapor-to liquid nucleation. In atmospheric sciences, as well as in other scientific fields, the theoretical treatment of nucleation is mostly based on a theory known as the Classical Nucleation Theory. However, the Classical Nucleation Theory is known to have only a limited success in predicting the rate at which vapor-to-liquid nucleation takes place at given conditions. This thesis studies the unary homogeneous vapor-to-liquid nucleation from a statistical mechanics viewpoint. We apply Monte Carlo simulations of molecular clusters to calculate the free energy barrier separating the vapor and liquid phases and compare our results against the laboratory measurements and Classical Nucleation Theory predictions. According to our results, the work of adding a monomer to a cluster in equilibrium vapour is accurately described by the liquid drop model applied by the Classical Nucleation Theory, once the clusters are larger than some threshold size. The threshold cluster sizes contain only a few or some tens of molecules depending on the interaction potential and temperature. However, the error made in modeling the smallest of clusters as liquid drops results in an erroneous absolute value for the cluster work of formation throughout the size range, as predicted by the McGraw-Laaksonen scaling law. By calculating correction factors to Classical Nucleation Theory predictions for the nucleation barriers of argon and water, we show that the corrected predictions produce nucleation rates that are in good comparison with experiments. For the smallest clusters, the deviation between the simulation results and the liquid drop values are accurately modelled by the low order virial coefficients at modest temperatures and vapour densities, or in other words, in the validity range of the non-interacting cluster theory by Frenkel, Band and Bilj. Our results do not indicate a need for a size dependent replacement free energy correction. The results also indicate that Classical Nucleation Theory predicts the size of the critical cluster correctly. We also presents a new method for the calculation of the equilibrium vapour density, surface tension size dependence and planar surface tension directly from cluster simulations. We also show how the size dependence of the cluster surface tension in equimolar surface is a function of virial coefficients, a result confirmed by our cluster simulations.

Scalable non-linear Support Vector Machine using hierarchical clustering

This paper discusses a method for scaling SVM with Gaussian kernel function to handle large data sets by using a selective sampling strategy for the training set. It employs a scalable hierarchical clustering algorithm to construct cluster indexing structures of the training data in the kernel induced feature space. These are then used for selective sampling of the training data for SVM to impart scalability to the training process. Empirical studies made on real world data sets show that the proposed strategy performs well on large data sets.

Critical age-dependent branching Markov processes and their scaling limits

This paper studies:(i)the long-time behaviour of the empirical distribution of age and normalized position of an age-dependent critical branching Markov process conditioned on non-extinction;and (ii) the super-process limit of a sequence of age-dependent critical branching Brownian motions.

Design of temperature-compensated reference electrodes for non-isothermal galvanic sensors

The criterion for the design of a temperature-compensated reference electrode for non-isothermal galvanic sensors is deduced from the basic flux equations of irreversible thermodynamics. It is shown that when the Seebeck coefficient of the non-isothermal cell using a solid oxygen ion-conducting electrolyte under pure oxygen is equal to the relative partial molar entropy of oxygen in the reference electrode divided by 4F, then the EMF of the non-isothermal cell is the same as that of an isothermal cell with the same electrodes operating at the higher temperature. By measuring the temperature of the melt alone and the EMF of the non-isothermal galvanic sensor, one can derive the chemical potential or the concentration of oxygen in a corrosive medium. The theory is experimentally checked using sensors for oxygen in liquid copper constructed with various metal+oxide electrodes and fully stabilised (CaO)ZrO2 as the electrolyte. To satisfy the exact condition for temperature compensation it is often necessary to have the metal or oxide as a solid solution in the reference electrode.

Molecular hydrodynamic theory of non‐Markovian collective orientational relaxation in dense dipolar liquids

A microscopic study of the non‐Markovian (or memory) effects on the collective orientational relaxation in a dense dipolar liquid is carried out by using an extended hydrodynamic approach which provides a reliable description of the dynamical processes occuring at the molecular length scales. Detailed calculations of the wave‐vector dependent orientational correlation functions are presented. The memory effects are found to play an important role; the non‐Markovian results differ considerably from that of the Markovian theory. In particular, a slow long‐time decay of the longitudinal orientational correlation function is observed for dense liquids which becomes weaker in the presence of a sizeable translational contribution to the collective orientational relaxation. This slow decay can be attributed to the intermolecular correlations at the molecular length scales. The longitudinal component of the orientational correlation function becomes oscillatory in the underdamped limit of momenta relaxations and the frequency dependence of the friction reduce the frictional resistance on the collective excitations (commonly known as dipolarons) to make them long lived. The theory predicts that these dipolarons can, therefore, be important in chemical relaxation processes, in contradiction to the claims of some earlier theoretical studies.

Impurity effects on the critical behaviour of the electrical resistance of binary liquid mixtures

The electrical resistance of the binary liquid system cyclohexane + acetic anhydride is measured, in the critical region, both in the pure mixture and when the mixture is doped with small amounts (≈ 100 ppm) of H2O/D2O impurities.T c was approached to aboutt=3×10−6 wheret=(T −T c )/T c . The critical exponentb ≈ 0.35 in the fit of the resistance data to the equationdR/dT ∼t −b does not seem to be affected appreciably by the impurities. There is a sign reversal ofdR/dt in the non-critical region. Binary liquid systems seem to violate the universality of the critical resistivity.

Microscopic theory of solvation of an ion in a binary dipolar liquid

A microscopic theory of the statics and the dynamics of solvation of an ion in a binary dipolar liquid is presented. The theory properly includes the different intermolecular correlations that are present in a binary mixture. As a result, the theory can explain several important aspects of both the statics and the dynamics of solvation that are observed in experiments. It provides a microscopic explanation of the preferential solvation of the more polar species by the solute ion. The dynamics of solvation is predicted to be highly non-exponential, in general. The average relaxation time is found to change nonlinearly with the composition of the mixture. These predictions are in qualitative agreement with the experimental results.

Bound states of two spin-1/2 fermions in a synthetic non-Abelian gauge field

We study the bound states of two spin-1/2 fermions interacting via a contact attraction (characterized by a scattering length) in the singlet channel in three-dimensional space in presence of a uniform non-Abelian gauge field. The configuration of the gauge field that generates a Rashba-type spin-orbit interaction is described by three coupling parameters (lambda(x),lambda(y),lambda(z)). For a generic gauge field configuration, the critical scattering length required for the formation of a bound state is negative, i.e., shifts to the ``BCS side'' of the resonance. Interestingly, we find that there are special high-symmetry configurations (e.g., lambda(x) = lambda(y) = lambda(z)) for which there is a two-body bound state for any scattering length however small and negative. Remarkably, the bound-state wave functions obtained for such configurations have nematic spin structure similar to those found in liquid He-3. Our results show that the BCS-BEC (Bose-Einstein condensation) crossover is drastically affected by the presence of a non-Abelian gauge field. We discuss possible experimental signatures of our findings both at high and low temperatures.

Prediction of nonlocal scaling parameter for armchair and zigzag single-walled carbon nanotubes based on molecular structural mechanics, nonlocal elasticity and wave propagation

Atomic vibration in the Carbon Nanotubes (CNTs) gives rise to non-local interactions. In this paper, an expression for the non-local scaling parameter is derived as a function of the geometric and electronic properties of the rolled graphene sheet in single-walled CNTs. A self-consistent method is developed for the linearization of the problem of ultrasonic wave propagation in CNTs. We show that (i) the general three-dimensional elastic problem leads to a single non-local scaling parameter (e(0)), (ii) e(0) is almost constant irrespective of chirality of CNT in the case of longitudinal wave propagation, (iii) e(0) is a linear function of diameter of CNT for the case of torsional mode of wave propagation, (iv) e(0) in the case of coupled longitudinal-torsional modes of wave propagation, is a function which exponentially converges to that of axial mode at large diameters and to torsional mode at smaller diameters. These results are valid in the long-wavelength limit. (C) 2011 Elsevier Ltd. All rights reserved.