Solvation dynamics in liquid water. A novel interplay between librational and diffusive modes

A microscopic calculation of the solvation dynamics of an ion in liquid water is presented. The calculated solvation time correlation function shows an ultrafast Gaussian decay which carries about 70%–90% of the strength followed by a biexponential decay with time constants equal to 250 fs and 1 ps. These results are in excellent agreement with the computer simulations of Maroncelli and Fleming and also with the experimental findings of Barbara and Jarzeba. In addition, we find that both the rotational librations and the intermolecular translational vibrational modes of water contribute significantly to the initial Gaussian decay.

The Determination of the Surface Tensions of Liquid-Iron, Nickel and Iron-Nickel Alloys using the electromagnetic Oscillating Droplet Technique

An oscillating droplet method combined with electromagnetic levitation has been applied to determine the surface tensions of liquid pure iron, nickel and iron-nickel alloys as a function of the temperature. The natural frequency of the oscillating droplet is evaluated using a Fourier analyser. The theoretical background of this method and the experimental set-up were described, and the influence of magnetic field strength was also discussed. The experimental results were compared with those of other investigators and interpreted using theoretical models (Butler's equation, subregular and perfect solution model for the surface phase).

Theory of the non-Fermi-liquid transition point in the two-impurity Kondo model

We present an explicit solution of the problem of two coupled spin-1/2 impurities, interacting with a band of conduction electrons. We obtain an exact effective bosonized Hamiltonian, which is then treated by two different methods (low-energy theory and mean-field approach). Scale invariance is explicitly shown at the quantum critical point. The staggered susceptibility behaves like ln(T(K)/T) at low T, whereas the magnetic susceptibility and [S1.S2] are well behaved at the transition. The divergence of C(T)/T when approaching the transition point is also studied. The non-Fermi-liquid (actually marginal-Fermi-liquid) critical point is shown to arise because of the existence of anomalous correlations, which lead to degeneracies between bosonic and fermionic states of the system. The methods developed in this paper are of interest for studying more physically relevant models, for instance, for high-T(c) cuprates.

Friction-formed liquid droplets

The formation of nanoscale liquid droplets by friction of a solid is observed in real-time. This is achieved using a newly developed in situ transmission electron microscope (TEM) triboprobe capable of applying multiple reciprocating wear cycles to a nanoscale surface. Dynamical imaging of the nanoscale cyclic rubbing of a focused-ion-beam (FIB) processed Al alloy by diamond shows that the generation of nanoscale wear particles is followed by a phase separation to form liquid Ga nanodroplets and liquid bridges. The transformation of a two-body system to a four-body solid-liquid system within the reciprocating wear track significantly alters the local dynamical friction and wear processes. Moving liquid bridges are observed in situ to play a key role at the sliding nanocontact, interacting strongly with the highly mobile nanoparticle debris. In situ imaging demonstrates that both static and moving liquid droplets exhibit asymmetric menisci due to nanoscale surface roughness. Nanodroplet kinetics are furthermore dependent on local frictional temperature, with solid-like surface nanofilaments forming on cooling. TEM nanotribology opens up new avenues for the real-time quantification of cyclic friction, wear and dynamic solid-liquid nanomechanics, which will have widespread applications in many areas of nanoscience and nanotechnology.

Parallel Tempering Simulations of Liquid-Phase Adsorption of n-Alkane Mixtures in Zeolite LTA-5A

Adsorption of n-alkane mixtures in the zeolite LTA-5A under liquid-phase conditions has been studied using grand canonical Monte Carlo (GCMC) simulations combined with parallel tempering. Normal GCMC techniques fail for some of these systems due to the preference of linear molecules to coil within a single cage in the zeolite. The narrow zeolite windows severerly restrict interactions of the molecules, making it difficult to simulate cooperative rearrangements necessary to explore configuration space. Because of these reasons, normal GCMC simulations results show poor reproducibility in some cases. These problems were overcome with parallel tempering techniques. Even with parallel tempering, these are very challenging systems for molecular simulation. Similar problems may arise for other zeolites such as CHA, AFX, ERI, KFI, and RHO having cages connected by narrow windows. The simulations capture the complex selectivity behavior observed in experiments such as selectivity inversion and azeotrope formation.

Crystallography of solid-liquid interface and evolution of texture during directional solidification of Tb0.3Dy0.7Fe1.95 alloy

The effect of growth texture on the magnetostriction of ternary Tb0.3Dy0.7Fe1.95 was studied by conducting unidirectional solidification experiments using a zoning set-up. Detailed texture evolutions were studied using X-ray diffraction on samples obtained by varying growth rates from 18 to 72 cm/h, under a temperature gradient of 100 degrees C/cm. The estimated texture co-efficient and pole figures of the samples indicate that during the onset of the solidification, < 110 > and < 331 >/'rotated < 110 >' texture components nucleate and grow in all the samples. However, as the solidification progresses, < 112 > texture component becomes dominant at higher growth rate. This results in an improvement of magnetostriction from 1000 to 1300 microstrains for samples grown at growth rates of 18 and 72 cm/h respectively. The transition of preferred growth direction occurs through intermediate orientations < 123 >. An attempt has been made in this paper to explain the occurrence of different growth texture by considering the stability of growing interface, its planar packing fraction and atomic stacking sequence of several low index planes. (C) 2010 Elsevier Ltd. All rights reserved.

Liquid-Liquid Interphase (Biphasic) as the Reaction Medium in the Assembly of a Hierarchy of Structures of 4,4 `-Azodibenzoic Acid with Zinc and Cadmium

The compounds Zn(C12H8N2)](2)C12N2H8(COO)(2)](2)center dot(C6H12O)center dot(H2O), I, Zn(C12H8N2)]C12N2H8(COO)(2)], II, Cd(C12H8N2)(H2O)]C12N2H8(COO)(2)]center dot(H2O), III, Zn(C10N2H8)]C12N2H8(COO)(2)]center dot 0.5(C10N2H8), IV, Cd(C12N2H8(COO)(2)center dot H2O], V, and Zn-3(mu(2)-O)(mu(3)-O)(3)]C12N2H8(COO)(2)], VI, have been synthesized by using a biphasic approach (I, III, V, VI) or regular hydrothermal method (II, IV). The compounds exhibit one (I and II), two (In), and three dimensionally (IV, V, VI) extended structures. The flexible azodibenzoate ligand gives rise to a 3-fold interpenetration (IV) when the synthesis was carried out using normal hydrothermal methods. The biphasic approach forms structures without any interpenetrations, especially in the three-dimensional structures of V and VI. Formation of Cd2O2 dimers in V and extended M-O(H)-M two-dimensional layers in VI suggests the subtle structural control achieved by the biphasic method. Transformation studies indicate that it is possible to transform I to II. Lewis acid catalytic studies have been performed to evaluate the role of the coordination environment in such reactions. All the compounds have been characterized by a variety of techniques that includes powder X-ray diffraction, infrared, thermogravitric analysis, UV-vis, photoluminescence studies.

Conductance of Tomonaga-Luttinger liquid wires and junctions with resistances

We study the effect that resistive regions have on the conductance of a quantum wire with interacting electrons which is connected to Fermi liquid leads. Using the bosonization formalism and a Rayleigh dissipation function to model the power dissipation, we use both scattering theory and Green's function techniques to derive the DC conductance. The resistive regions are generally found to lead to incoherent transport. For a single wire, we find that the resistance adds in series to the contact resistance of h/e(2) for spinless electrons, and the total resistance is independent of the Luttinger parameter K-W of the wire. We numerically solve the bosonic equations to illustrate what happens when a charge density pulse is incident on the wire; the results depend on the parameters of the resistive and interacting regions in interesting ways. For a junction of Tomonaga-Luttinger liquid wires, we use a dissipationless current splitting matrix to model the junction. For a junction of three wires connected to Fermi liquid leads, there are two families of such matrices; we find that the conductance matrix generally depends on K-W for one family but is independent of K-W for the other family, regardless of the resistances present in the system. Copyright (c) EPLA, 2011

Heavy-metal removal using liquid membrane

Experiments have been conducted to obtain the optimum conditions of hydrogen ion concentration of feed and strip phases and concentration of the carrier ALAMINE 336, in the extraction of Cr(VI) and Hg(II) using two different types of liquid membranes-bulk liquid membrane and emulsion liquid membrane. Experiments have also been carried out to find the effect of metal loading and the effect of extraction time on metal flux.

Ionic and dipolar solvation dynamics in liquid water

The solvation time correlation function for solvation in liquid water was measured recently. The solvation was found to be very fast, with a time constant equal to 55 fs. In this article we present theoretical studies on solvation dynamics of ionic and dipolar solutes in liquid water, based on the molecular hydrodynamic approach developed earlier. The molecular hydrodynamic theory can successfully predict the ultrafast dynamics of solvation in liquid water as observed from recent experiments. The present study also reveals some interesting aspects of dipolar solvation dynamics, which differs significantly from that of ionic solvation.

Non-Fermi liquid behavior in a mean-field study of the t-J model: Role of zero-point spin fluctuations

We present analytic results to show that the Schwinger-boson hole-fermion mean-field state exhibits non-Fermi liquid behavior due to spin-charge separation. The physical electron Green's function consists of three additive components. (a) A Fermi-liquid component associated with the bose condensate. (b) A non-Fermi liquid component which has a logarithmic peak and a long tail that gives rise to a linear density of states that is symmetric about the Fermi level and a momentum distribution function with a logarithmic discontinuity at the Fermi surface. (c) A second non-Fermi liquid component associated with the thermal bosons which leads to a constant density of states. It is shown that zero-point fluctuations associated with the spin-degrees of freedom are responsible for the logarithmic instabilities and the restoration of particle-hole symmetry close to the Fermi surface.

Orientational Order of Liquid-Crystalline 4-Alkyl-N-(p-cyanophenyl)piperidines by 2H and 13C NMR Spectroscopies

The orientational order of nematic 4-alkyl-N-(4-cyanophenyl) piperidines (I) has been determined from H-2 and C-13 NMR spectra. Molecular-order parameters are derived from the carbon-13 chemical shift of the cyano carbon atom in the nematic and the isotropic phases; the sign of the diamagnetic anisotropy is positive. Deuterium quadrupolar splittings from the partially deuterated piperidine ring of I are then related to various C-D bonds.

Crossover dynamics at large metastability in gas-liquid nucleation

We have developed an alternate description of dynamics of nucleation in terms of an extended set of order parameters. The order parameters consist of an ordered set of kth largest clusters, ordered such that k = 1 is the largest cluster in the system, k = 2 is the second largest cluster, and so on. We have derived an analytic expression for the free energy for the kth largest cluster, which is in excellent agreement with the simulated results. At large supersaturation, the free energy barrier for the growth of the kth largest cluster disappears and the nucleation becomes barrierless. The major success of this extended theoretical formalism is that it can clearly explain the observed change in mechanism at large metastability P. Bhimalapuram et al., Phys. Rev. Lett. 98, 206104 (2007)] and the associated dynamical crossover. The classical nucleation theory cannot explain this crossover. The crossover from activated to barrierless nucleation is found to occur at a supersaturation where multiple clusters cross the critical size. We attribute the crossover as the onset of the kinetic spinodal. We have derived an expression for the rate of nucleation in the barrierless regime by modeling growth as diffusion on the free energy surface of the largest cluster. The model reproduces the slower increase in the rate of growth as a function of supersaturation, as observed in experiments.

C-13 MAS NMR spectra of cis,cis-mucononitrile in liquid-crystalline media and in the solid state. Orientation of the carbon chemical-shift tensors

The spinning sidebands observed in the C-13 MAS NMR spectra of cis,cis-mucononitrile oriented in liquid-crystalline media and of the neat sample in the solid state are studied. There are differences in the sideband intensity patterns in the two cases. These differences arise because the order parameters which characterize the orientation of the solute in the liquid-crystalline media differ for different axes. It is shown that, in general, the relative intensities of the sidebands contain information on the sign and magnitude of an effective chemical-shift parameter which is a function of the sum of the products of the principal components of the chemical-shift tensor and the corresponding order parameters with respect to the director. A method for obtaining the orientation of the carbon chemical-shift tensor is proposed. The carbon chemical-shift tensors obtained from gauge-including atomic orbital calculations are also presented for comparison. (C) 1996 Academic Press, Inc.