Search results for "THERMODYNAMICS"
showing 10 items of 2774 documents
Volumetric properties, viscosities and refractive indices of binary liquid mixtures of tetrafluoroborate-based ionic liquids with methanol at several…
2015
Abstract Densities, speeds of sound, viscosities and refractive indices of two binary systems 1-butyl-3-methylimidazolium tetrafluoroborate [bmim][BF4] + methanol and 1-ethyl-3-methylimidazolium tetrafluoroborate [emim][BF4] + methanol, as well as of all pure components, have been measured covering the whole range of compositions at T = (278.15 to 318.15) K and p = 101 kPa. From this data, excess molar volumes, excess isentropic compressibilities, viscosity deviations and refractive index deviations were calculated and fitted to extended versions of the Redlich–Kister equation. Estimated coefficients of these equations taking into account the dependence on composition and temperature simult…
Crystal growth and phase transitions of solid solutions in [N(CH3)4]2MX4 isomorph class
1989
Abstract Homogeneous single crystals of tetramethylammonium tetrahalogenometallate solid solutions have been grown: a temperature difference growth method with thermally enforced convection was used during the material transport from an equilibrated feed material to the growing crystals. The smallest crystals were mostly studied by differential scanning calorimetry and X-ray crystallography. Some bigger crystals were available for dielectric measurements and Raman scattering. The temperature-concentration phase diagrams of solid solutions look like the temperature-pressure phase diagrams of pure tetramethylammonium salts. The progressive substitution seems equivalent to a change of the pres…
Conformation of a chain polyelectrolyte in solution with low molecular weight salt: small angle neutron scattering measurements
1986
Small angle neutron scattering measurements have been carried out on the tetramethylammonium salt of the polystyrenesulfonic acid withDP w =310 and 1060 in water solution with tetramethylammonium chloride with ionic strength between 0.02 M and 1.0 M. The scattering curves in the scattering vector range 0.05 nm−1≤Q≤1.8nm−1 have been fitted using the form factor of a worm-like chain of finite thickness. The conformational parameters mean square radius of gyration, statistic chain element, mass per unit length and mean square radius of the cross-section have been determined experimentally and used for describing the conformation of the coils. By these molecular weights and ionic strengths, exc…
New QM/MM implementation of the DFTB3 method in the gromacs package.
2015
The approximate density-functional tight-binding theory method DFTB3 has been implemented in the quantum mechanics/molecular mechanics (QM/MM) framework of the Gromacs molecular simulation package. We show that the efficient smooth particle–mesh Ewald implementation of Gromacs extends to the calculation of QM/MM electrostatic interactions. Further, we make use of the various free-energy functionalities provided by Gromacs and the PLUMED plugin. We exploit the versatility and performance of the current framework in three typical applications of QM/MM methods to solve biophysical problems: (i) ultrafast proton transfer in malonaldehyde, (ii) conformation of the alanine dipeptide, and (iii) el…
Study of the ZnO crystal growth by vapour transport methods
2004
Abstract The crystal growth of ZnO by vapour transport is classically made with the assistance of additional species that produce a gaseous mixture, the role of which remains often uncertain in the transport and growth process. Initially, in order to study the mass transport process, a numerical simulation is made to analyse which are the requirements to have an effective transport. As the pressure of each gaseous species is generally unknown, the numerical study has been performed for different total pressures. It is found that, if congruent and equilibrium conditions are assumed at the sublimation and crystallisation interfaces, effective growth conditions can only be attained for a narro…
Estimation of Nucleation Barriers from Simulations of Crystal Nuclei Surrounded by Fluid in Equilibrium
2016
Nucleation rates for homogeneous nucleation are commonly estimated in terms of an Arrhenius law involving the nucleation barrier, written in terms of a competition of the contribution in surface free energy of the nucleus and the free energy gain proportional to the nucleus volume. For crystal nuclei this “classical nucleation theory” is hampered by the problem that the nucleus in general is non spherical, since the interfacial excess free energy depends on the orientation of the interface relative to the crystal axes. This problem can be avoided by analyzing the equilibrium of a crystal nucleus surrounded by fluid in a small simulation box in thermal equilibrium. Estimating the fluid press…
Determination of cluster binding energies on metal surfaces by statistics
2000
Abstract Two simple formulae to determine binding energies of two-dimensional clusters on surfaces in thermal equilibrium are derived. One requires measurement of monomer and cluster populations and of the surface temperature. The cluster dissociation rate is derived and related to the atom hopping rate, allowing the theory to be extended to adatom populations that are not in chemical equilibrium. The result gives a recipe for determining dissociation energies that requires measurements of only two rates at a single temperature.
Thermoconvective instability and local thermal non-equilibrium in a porous layer with isoflux-isothermal boundary conditions
2014
The effects of lack of local thermal equilibrium between the solid phase and the fluid phase are taken into account for the convective stability analysis of a horizontal porous layer. The layer is bounded by a pair of plane parallel walls which are impermeable and such that the lower wall is subject to a uniform flux heating, while the upper wall is isothermal. The local thermal non-equilibrium is modelled through a two-temperature formulation of the energy exchange between the phases, resulting in a pair of local energy balance equations: one for each phase. Small-amplitude disturbances of the basic rest state are envisaged to test the stability. Then, the standard normal mode procedure is…
Aging effects in simple models for glassy relaxation
2006
Aging effects in the two-time correlation function and the response function after a quench from a high temperature to some low temperature are considered for a simple kinetic random energy model exhibiting stretched exponential relaxation. Because the system reaches thermal equilibrium for long times after the quench, all aging effect are of a transient nature. In particular, the violations of the fluctuation-dissipation theorem are considered and it is found that the relation between the response and the two-time correlation function depends on another function, the so-called asymmetry. This asymmetry vanishes in equilibrium but cannot be neglected in the aging regime. It is found that pl…
Indium-Gallium Segregation inCuInxGa1−xSe2: AnAb Initio–Based Monte Carlo Study
2010
Thin-film solar cells with ${\mathrm{CuIn}}_{x}{\mathrm{Ga}}_{1\ensuremath{-}x}{\mathrm{Se}}_{2}$ (CIGS) absorber are still far below their efficiency limit, although lab cells already reach 20.1%. One important aspect is the homogeneity of the alloy. Large-scale simulations combining Monte Carlo and density functional calculations show that two phases coexist in thermal equilibrium below room temperature. Only at higher temperatures, CIGS becomes more and more a homogeneous alloy. A larger degree of inhomogeneity for Ga-rich CIGS persists over a wide temperature range, which contributes to the observed low efficiency of Ga-rich CIGS solar cells.