Solution calorimetry of organic nonelectrolytes as a tool for investigation of intermolecular interactions

The paper is mainly the review and generalization of the previous publications of the authors. It demonstrates that solution calorimetry method gives the opportunities of more detailed understanding of various aspects of intermolecular interactions in solution. We are assured that prerequisite to such an understanding is the successive analysis of various solute–solvent systems from the simplest ones which include alkanes as a solute or as a solvent to the most complex systems with solvent self‐association via hydrogen bonding. Particular findings discussed in this paper are (i) an inconspicuous contribution of electrostatic solute–solvent interaction to the solvation enthalpy and, accordingly, the dominating contribution of dispersion interactions for nonspecifically solvated solutes; (ii) new, very general method for the extraction of specific interaction enthalpy from the enthalpy of solvation; (iii) new method of determination of self‐association enthalpies for the solvents associated via hydrogen bonding; (iv) new method for determination of cooperative hydrogen bonding enthalpies of proton acceptors with associated species of alcohols; (v) the unique method of experimental determination of the hydrophobic effect enthalpy. Copyright © 2007 John Wiley & Sons, Ltd.     

Gold chloride cluster ions generated by vacuum laser ablation

In this work, a simple way for study the possibility of formation a vapor cluster species of tetrachloroauric acid (HAuCl₄), using the laser ablation in the absence of a buffer or reactive atmosphere, and without a postablation supersonic expansion on a commercial matrix assisted laser desorption/ionization time-of-flight mass spectrometer, is reported. Tetrachloroauric acid is known as precursor for the synthesis of gold nanostructures and the complex salts; therefore it is an important task to discover and quantify the species arising from HAuCl₄, in order to understand their role in the gold assisted reactions. Mass spectrum of HAuCl₄ in a reflector negative-ion mode contains the hydrated mono- and dinuclear gold clusters in the m/z range 286–436, and gold chloride clusters in the m/z range 447–795. In the first part of spectrum, m/z range 286–436, the hydrated gold cluster species of type Au _n ^? (H₂O)_m (n?=?1–2; m?=?1, 2, 5, 7, 8) and [Au_n(OH)_k]^?(H₂O)_m (n?=?1–2; k?=?1–2; m?=?1, 4–8) were found. Besides that, there are gold chloride clusters with general formula [AuH_r(HCl)₂]^?(H₂O)_m (m?=?1–5; 8–9; r?=?0–2) in this part of spectrum. In the second part of spectrum, the m/z range 447–795, only gold chloride clusters were obtained. Their general formulae can be written as [AuCl_t(HCl)_v]^?(H₂O)_m (t?=?1–4; v?=?5–8; m?=?2–4, 6–8) and [Au_n(HCl)_v]^?(H₂O)_m (n?=?1–2, v?=?4–5, m?=?1–2, 5, 7). The analysis of concentration effects on the LDI mass spectra of gold clusters reveals that the relative intensities of signals for the mono- and dinuclear Au clusters increase with decreasing the concentration of water HAuCl₄ solutions.     

Baryon asymmetry of the proton sea at low-x

We predict a nonvanishing baryon asymmetry of the proton sea at low x. It is expected to be about 7% and nearly x-independent at x < 0.5 × 10^-3. The asymmetry arises from the baryon-antibaryon component of the Pomeron, rather than from the valence quarks of the proton, which are wide believed carriers of baryon number. Experimental study of x-distribution of the baryon asymmetry of the proton sea can be performed in ep or γp interactions at HERA, where x ～ 10^-5 are reachable, smaller than at any of existing or planned proton colliders.     

Just noticeable differences of open quotient and asymmetry coefficient in singing voice

This study aims to explore the perceptual relevance of the variations of glottal flow parameters and to what extent a small variation can be detected. Just Noticeable Differences (JNDs) have been measured for three values of open quotient (0.4, 0.6, and 0.8) and two values of asymmetry coefficient (2/3 and 0.8), and the effect of changes of vowel, pitch, vibrato, and amplitude parameters has been tested. Two main groups of subjects have been analyzed: a group of 20 untrained subjects and a group of 10 trained subjects. The results show that the JND for open quotient is highly dependent on the target value: an increase of the JND is noticed when the open quotient target value is increased. The relative JND is constant: ΔO_q/O_q = 14% for the untrained and 10% for the trained. In the same way, the JND for asymmetry coefficient is also slightly dependent on the target value–an increase of the asymmetry coefficient value leads to a decrease of the JND. The results show that there is no effect from the selected vowel or frequency (two values have been tested), but that the addition of a vibrato has a small effect on the JND of open quotient. The choice of an amplitude parameter also has a great effect on the JND of open quotient.     

Stability of an encapsulated bubble shell

The stability of an encapsulated bubble filled with gas is studied where gas is allowed to diffuse out of the bubble. A mechanistic model that takes into account shell stiffness and surface tension is considered. A critical shell radius for loss of mechanical stability is derived based on a technique adapted for small radius, where surface tension effects become substantial. A new parameter is defined that determines the relative importance of surface tension forces and shell stiffness for shell stability. The developed technique allows to predict, for a given bubble population and gas saturation level of the surrounding liquid, a range of bubble sizes which may collapse in time. Surface tension effects are dominant in determining the critical radius but have a negligible effect on the minimal radius for collapse. The influence of the surface tension on the stability of the shell is illustrated for Optison, a typical ultrasound contrast agent.     

Sharp Lower Bounds for the Dimension of the Global Attractor of the Sabra Shell Model of Turbulence

In this work we derive lower bounds for the Hausdorff and fractal dimensions of the global attractor of the Sabra shell model of turbulence in different regimes of parameters. We show that for a particular choice of the forcing term and for sufficiently small viscosity term ν, the Sabra shell model has a global attractor of large Hausdorff and fractal dimensions proportional to log  ν ⁻¹ for all values of the governing parameter ε, except for ε =1. The obtained lower bounds are sharp, matching the upper bounds for the dimension of the global attractor obtained in our previous work. Moreover, the complexity of the dynamics of the shell model increases as the viscosity ν tends to zero, and we describe a precise scenario of successive bifurcations for different parameters regimes. In the “three-dimensional” regime of parameters this scenario changes when the parameter ε becomes sufficiently close to 0 or to 1. We also show that in the “two-dimensional” regime of parameters, for a certain non-zero forcing term, the long-term dynamics of the model becomes trivial for every value of the viscosity. AMS Subject Classifications: 76F20, 76D05, 35Q30     

Highly resolved fluid flows: "liquid plasmas" at the kinetic level

Fluid flow around an obstacle was observed at the kinetic (individual particle) level using "complex (dusty) plasmas" in their liquid state. These "liquid plasmas" have bulk properties similar to water (e.g., viscosity), and a comparison in terms of similarity parameters suggests that they can provide a unique tool to model classical fluids. This allows us to study "nanofluidics" at the most elementary-the particle-level, including the transition from fluid behavior to purely kinetic transport. In this (first) experimental investigation we describe the kinetic flow topology, discuss our observations in terms of fluid theories, and follow this up with numerical simulations.     

Superfluid-superfluid phase transitions in a two-component Bose-Einstein condensate

Depending on the Hamiltonian parameters, two-component bosons in an optical lattice can form at least three different superfluid phases in which both components participate in the superflow: a (strongly interacting) mixture of two miscible superfluids (2SF), a paired superfluid (PSF) vacuum, and (at a commensurate total filling factor) the super-counter-fluid (SCF) state. We study the universal properties of the 2SF-PSF and 2SF-SCF quantum phase transitions and show that (i) they can be mapped onto each other and (ii) their universality class is identical to the (d+1)-dimensional normal-superfluid transition in a single-component liquid. The finite-temperature 2SF-PSF(SCF) transitions and the topological properties of 2SF-PSF(SCF) interfaces are also discussed.     

Peculiarities of magnetic,galvanomagnetic, elastic,and magnetoelastic properties of Eu<Subscript>0.55</Subscript>Sr<Subscript>0.45</Subscript>MnO<Subscript>3</Subscript>

Magnetic, elastic, magnetoelastic, transport, and magnetotransport properties of the Eu_0.55Sr_0.45MnO₃ ceramics have been studied. A break was detected in the temperature dependence of electrical resistivity ρ(T) near the temperature of the magnetic phase transformation (41 K), with the material remaining an insulator down to the lowest measurement temperature reached (ρ=10⁶ Ω cm at 4.2 K). In the interval 4.2≤T≤50 K, the isotherms of the magnetization, volume magnetostriction, and ρ were observed to undergo jumps at the critical field H_C1, which decreases with increasing T. For 50≤T≤120 K, the jumps in the above curves persist, but the pattern of the curves changes and H_C1 grows with increasing T. The magnetoresistance Δρ/ρ = (ρ _H ?ρ_H=0)/ρ _H is positive for H<H_C1 and passes through a maximum at 41 K, where Δρ/ρ = 6%. For H>H_C1, the magnetoresistance is negative, passes through a minimum near 41 K, and reaches a colossal value of 3×10⁵ % at H=45 kOe. The volume magnetostriction is negative and attains a giant value of 4.5×10^?4atH=45 kOe. The observed properties are assigned to the existence of three phases in Eu_0.55Sr_0.45MnO₃, namely, a ferromagnetic (FM) phase, in which carriers are concentrated because of the gain in s-d exchange energy, and two antiferromagnetic (AFM) phases of the A and CE types. Their fractional volumes at low temperatures were estimated to be as follows: ～3% of the sample volume is occupied by the FM phase; ～67%, by the CE-type AFM phase; and ～30%, by the A-type AFM phase.     

Optoacoustic solitons in Bragg gratings

Optical gap solitons, which exist due to a balance of nonlinearity and dispersion due to a Bragg grating, can couple to acoustic waves through electrostriction. This gives rise to a new species of "gap-acoustic" solitons (GASs), for which we find exact analytic solutions. The GAS consists of an optical pulse similar to the optical gap soliton, dressed by an accompanying phonon pulse. Close to the speed of sound, the phonon component is large. In subsonic (supersonic) solitons, the phonon pulse is a positive (negative) density variation. Coupling to the acoustic field damps the solitons' oscillatory instability, and gives rise to a distinct instability for supersonic solitons, which may make the GAS decelerate and change direction, ultimately making the soliton subsonic.