Subquadratic quantum number dependence and other anomalies of vibrational dephasing in liquid nitrogen: Molecular dynamics simulation study from the triple point to the critical point and beyond

Vibrational phase relaxation near gas-liquid and liquid-solid phase coexistence has been studied by molecular dynamics simulations of N-N stretch in N-2. Experimentally observed pronounced insensitivity of phase relaxation from the triple point to beyond the boiling point is found to originate from a competition between density relaxation and resonant-energy transfer terms. The sharp rise in relaxation rate near the critical point (CP) can be attributed at least partly to the sharp, rise in vibration-rotation coupling contribution. Substantial subquadratic quantum number dependence of overtone dephasing rate is found near the CP and in supercritical fluids. [S0031-9007 (99)09318-7].

Field and potential around local scatterers in thin metal films studied by scanning tunneling potentiometry

We report the direct observation of electrochemical potential and local transport field variations near scatterers like grain boundaries, triple points, and voids in thin platinum films studied by scanning tunneling potentiometry. The field is highest at a void, followed by a triple point and a grain boundary. The local transport field near a void can even be four orders of magnitude higher than the macroscopic field, indicating that the void is the most likely place for an electromigration induced failure. The field build up for a particular type of scatterer depends on the grain connectivity. We estimate an average grain boundary reflection coefficient for the film from the temperature dependence of its resistivity.

The relation between polarisation and electric field for trissarcosine calcium chloride

Measurement of the relation between polarisation and electric field for ferroelectric trissarcosine calcium chloride (TSCC) was made in the pressure range up to 6 kbar. The pressure dependence of the spontaneous polarisation and the coercive field were obtained, and the existence of a new pressure-induced phase and the paraelectric- ferroelectric-new phase triple point were found.

Theory of freezing in simple systems

The transition parameters for the freezing of two one-component liquids into crystalline solids are evaluated by two theoretical approaches. The first system considered is liquid sodium which crystallizes into a body-centered-cubic (bcc) lattice; the second system is the freezing of adhesive hard spheres into a face-centered-cubic (fcc) lattice. Two related theoretical techniques are used in this evaluation: One is based upon a recently developed bifurcation analysis; the other is based upon the theory of freezing developed by Ramakrishnan and Yussouff. For liquid sodium, where experimental information is available, the predictions of the two theories agree well with experiment and each other. The adhesive-hard-sphere system, which displays a triple point and can be used to fit some liquids accurately, shows a temperature dependence of the freezing parameters which is similar to Lennard-Jones systems. At very low temperature, the fractional density change on freezing shows a dramatic increase as a function of temperature indicating the importance of all the contributions due to the triplet direction correlation function. Also, we consider the freezing of a one-component liquid into a simple-cubic (sc) lattice by bifurcation analysis and show that this transition is highly unfavorable, independent of interatomic potential choice. The bifurcation diagrams for the three lattices considered are compared and found to be strikingly different. Finally, a new stability analysis of the bifurcation diagrams is presented.

Two-Phase Thermodynamic Model for Efficient and Accurate Absolute Entropy of Water from Molecular Dynamics Simulations

Presented here is the two-phase thermodynamic (2PT) model for the calculation of energy and entropy of molecular fluids from the trajectory of molecular dynamics (MD) simulations. In this method, the density of state (DoS) functions (including the normal modes of translation, rotation, and intramolecular vibration motions) are determined from the Fourier transform of the corresponding velocity autocorrelation functions. A fluidicity parameter (f), extracted from the thermodynamic state of the system derived from the same MD, is used to partition the translation and rotation modes into a diffusive, gas-like component (with 3Nf degrees of freedom) and a nondiffusive, solid-like component. The thermodynamic properties, including the absolute value of entropy, are then obtained by applying quantum statistics to the solid component and applying hard sphere/rigid rotor thermodynamics to the gas component. The 2PT method produces exact thermodynamic properties of the system in two limiting states: the nondiffusive solid state (where the fluidicity is zero) and the ideal gas state (where the fluidicity becomes unity). We examine the 2PT entropy for various water models (F3C, SPC, SPC/E, TIP3P, and TIP4P-Ew) at ambient conditions and find good agreement with literature results obtained based on other simulation techniques. We also validate the entropy of water in the liquid and vapor phases along the vapor-liquid equilibrium curve from the triple point to the critical point. We show that this method produces converged liquid phase entropy in tens of picoseconds, making it an efficient means for extracting thermodynamic properties from MD simulations.

Absolute Entropy and Energy of Carbon Dioxide Using the Two-Phase Thermodynamic Model

The two-phase thermodynamic (2PT) model is used to determine the absolute entropy and energy of carbon dioxide over a wide range of conditions from molecular dynamics trajectories. The 2PT method determines the thermodynamic properties by applying the proper statistical mechanical partition function to the normal modes of a fluid. The vibrational density of state (DoS), obtained from the Fourier transform of the velocity autocorrelation function, converges quickly, allowing the free energy, entropy, and other thermodynamic properties to be determined from short 20-ps MD trajectories. The anharmonic effects in the vibrations are accounted for by the broadening of the normal modes into bands from sampling the velocities over the trajectory. The low frequency diffusive modes, which lead to finite DoS at zero frequency, are accounted for by considering the DoS as a superposition of gas-phase and solid-phase components (two phases). The analytical decomposition of the DoS allows for an evaluation of properties contributed by different types of molecular motions. We show that this 2PT analysis leads to accurate predictions of entropy and energy of CO2 over a wide range of conditions (from the triple point to the critical point of both the vapor and the liquid phases along the saturation line). This allows the equation of state of CO2 to be determined, which is limited only by the accuracy of the force field. We also validated that the 2PT entropy agrees with that determined from thermodynamic integration, but 2PT requires only a fraction of the time. A complication for CO2 is that its equilibrium configuration is linear, which would have only two rotational modes, but during the dynamics it is never exactly linear, so that there is a third mode from rotational about the axis. In this work, we show how to treat such linear molecules in the 2PT framework.

Theory of Gas Hydrates: Effect of the Approximation of Rigid Water Lattice

One of the assumptions of the van der Waals and Platteeuw theory for gas hydrates is that the host water lattice is rigid and not distorted by the presence of guest molecules. In this work, we study the effect of this approximation on the triple-point lines of the gas hydrates. We calculate the triple-point lines of methane and ethane hydrates via Monte Carlo molecular simulations and compare the simulation results with the predictions of van der Waals and Platteeuw theory. Our study shows that even if the exact intermolecular potential between the guest molecules and water is known, the dissociation temperatures predicted by the theory are significantly higher. This has serious implications to the modeling of gas hydrate thermodynamics, and in spite of the several impressive efforts made toward obtaining an accurate description of intermolecular interactions in gas hydrates, the theory will suffer from the problem of robustness if the issue of movement of water molecules is not adequately addressed.

New physics in e(+)e(-) -> Z(gamma) at the ILC with polarized beams: explorations beyond conventional anomalous triple gauge boson couplings

One of the most-studied signals for physics beyond the standard model in the production of gauge bosons in electron-positron collisions is due to the anomalous triple gauge boson couplings in the Z(gamma) final state. In this work, we study the implications of this at the ILC with polarized beams for signals that go beyond traditional anomalous triple neutral gauge boson couplings. Here we report a dimension-8 CP-conserving Z(gamma)Z vertex that has not found mention in the literature. We carry out a systematic study of the anomalous couplings in general terms and arrive at a classification. We then obtain linear-order distributions with and without CP violation. Furthermore, we place the study in the context of general BSM interactions represented by e(+)e(-)Z(gamma) contact interactions. We set up a correspondence between the triple gauge boson couplings and the four-point contact interactions. We also present sensitivities on these anomalous couplings, which will be achievable at the ILC with realistic polarization and luminosity.

A new two point method of obtaining Cv from a consolidation test: Discussion

Careful study of various aspects presented in the note reveals basic fallacies in the concept and final conclusions.The Authors claim to have presented a new method of determining C-v. However, the note does not contain a new method. In fact, the method proposed is an attempt to generate settlement vs. time data using only two values of (t,8). The Authors have used a rectangular hyperbola method to determine C-v from the predicated 8- t data. In this context, the title of the paper itself is misleading and questionable. The Authors have compared C-v values predicated with measured values, both of them being the results of the rectangular hyperbola method.

Temperature dependent vibrational lifetimes in supercritical fluids near the critical point

Vibrational relaxation measurements on the CO asymmetric stretching mode (similar to 1980 cm(-1)) of tungsten hexacarbonyl (W(CO)(6)) as a function of temperature at constant density in several supercritical solvents in the vicinity of the critical point are presented. In supercritical ethane, at the critical density, there is a region above the critical temperature (Tc) in which the lifetime increases with increasing temperature. When the temperature is raised sufficiently (similar to T-c + 70 degrees C), the lifetime decreases with further increase in temperature. A recent hydrodynamic/thermodynamic theory of vibrational relaxation in supercritical fluids reproduces this behavior semiquantitatively. The temperature dependent data for fixed densities somewhat above and below the critical density is in better agreement with the theory. In fluoroform solvent at the critical density, the vibrational lifetime also initially increases with increasing temperature. However, in supercritical CO2 at the critical density, the temperature dependent vibrational lifetime decreases approximately linearly with temperature beginning almost immediately above T-c. The theory does not reproduce this behavior. A comparison between the absolute lifetimes in the three solvents and the temperature trends is made.

Unsteady free convection flow in the stagnation-point region of a rotating sphere

The unsteady free convection boundary-layer flow in the forward stagnation-point region of a sphere, which is rotating with time-dependent angular velocity in an ambient fluid, has been studied. Both constant wall temperature and constant hear flux conditions have been considered. The non-linear coupled parabolic partial differential equations governing the flow have been solved numerically using an implicit finite-difference scheme. The skin friction and the heat transfer are enhanced by the buoyancy force. The effect of the buoyancy force is found to be more pronounced for smaller Prandtl numbers than for larger Prandtl numbers. For a given buoyancy force, the heat transfer increases with an increase in Prandtl number, but the skin friction decreases.

Unsteady free convection flow in the stagnation-point region of a three-dimensional body

The unsteady free convection flow in the stagnation-point region of a heated three-dimensional body placed in an ambient fluid is studied under boundary layer approximations. We have considered the case where there is an initial steady state that is perturbed by a step-change in the wall temperature. The non-linear coupled partial differential equations governing the free convection flow are solved numerically using a finite difference scheme. The presented results show the temporal development of the momentum and thermal boundary layer characteristics.

Flow and heat transfer in a stagnation-point flow over a stretching sheet with a magnetic field

The flow and heat transfer problem in the boundary layer induced by a continuous moving surface is important in many manufacturing processes in industry such as the boundary layer along material handling conveyers, the aerodynamic extrusion of plastic sheet, the cooling of an infinite metalic plate in a cooling bath (which may also be electrolyte). Glass blowing, continuous casting and spinning of fibres also involve the flow due to a stretching surface. Sakiadis [1] was the first to study the flow induced by a semi-infinite moving wall in an ambient fluid. On the other hand, Crane [2] first studied the flow over a linearly stretching sheet in an ambient fluid. Subsequently, Crane [3] also investigated the corresponding heat transfer problem. Since then several authors [4-8] have studied various aspects of this problem such as the effects of mass transfer, variable wall temperature, constant heat flux, magnetic field etc. Recently, Andersson [9] has obtained an exact solution of the Navier-Stokes equations for the MHD flow over a linearly stretching sheet in an ambient fluid. Also Chiam [10] has studied the heat transfer with variable thermal conductivity on a stretching sheet when the velocities of the sheet and the free stream are equal.

Defect production due to quenching through a multicritical point

We study the generation of defects when a quantum spin system is quenched through a multicritical point by changing a parameter of the Hamiltonian as t/tau, where tau is the characteristic timescale of quenching. We argue that when a quantum system is quenched across a multicritical point, the density of defects (n) in the final state is not necessarily given by the Kibble-Zurek scaling form n similar to 1/tau(d nu)/((z nu+1)), where d is the spatial dimension, and. and z are respectively the correlation length and dynamical exponent associated with the quantum critical point. We propose a generalized scaling form of the defect density given by n similar to 1/(tau d/(2z2)), where the exponent z(2) determines the behavior of the off-diagonal term of the 2 x 2 Landau-Zener matrix at the multicritical point. This scaling is valid not only at a multicritical point but also at an ordinary critical point.

Micro-scale anaerobic digestion of point source components of organic fraction of municipal solid waste

The fermentation characteristics of six specific types of the organic fraction of municipal solid waste (OFMSW) were examined, with an emphasis on properties that are needed when designing plug-flow type anaerobic bioreactors. More specifically, the decomposition patterns of a vegetable (cabbage), fruits (banana and citrus peels), fresh leaf litter of bamboo and teak leaves, and paper (newsprint) waste streams as feedstocks were studied. Individual OFMSW components were placed into nylon mesh bags and subjected to various fermentation periods (solids retention time, SRT) within the inlet of a functioning plug-flow biogas fermentor. These were removed at periodic intervals, and their composition was analyzed to monitor decomposition rates and changes in chemical composition. Components like cabbage waste, banana peels, and orange peels fermented rapidly both in a plug-flow biogas reactor (PFBR) as well as under a biological methane potential (BMP) assay, while other OFMSW components (leaf litter from bamboo and teak leaves and newsprint) fermented slowly with poor process stability and moderate biodegradation. For fruit and vegetable wastes (FVW), a rapid and efficient removal of pectins is the main cause of rapid disintegration of these feedstocks, which left behind very little compost forming residues (2–5%). Teak and bamboo leaves and newsprint decomposed only to 25–50% in 30 d. These results confirm the potential for volatile fatty acids accumulation in a PFBR’s inlet and suggest a modification of the inlet zone or operation of a PFBR with the above feedstocks.