74 research outputs found
Nature of the metal-nonmetal transition in metal-ammonia solutions. I. Solvated electrons at low metal concentrations
Using a theory of polarizable fluids, we extend a variational treatment of an
excess electron to the many-electron case corresponding to finite metal
concentrations in metal-ammonia solutions (MAS). We evaluate dielectric,
optical, and thermodynamical properties of MAS at low metal concentrations. Our
semi-analytical calculations based on a mean-spherical approximation correlate
well with the experimental data on the concentration and the temperature
dependencies of the dielectric constant and the optical absorption spectrum.
The properties are found to be mainly determined by the induced dipolar
interactions between localized solvated electrons, which result in the two main
effects: the dispersion attractions between the electrons and a sharp increase
in the static dielectric constant of the solution. The first effect provides a
classical phase separation for the light alkali metal solutes (Li, Na, K) below
a critical temperature. The second effect leads to a dielectric instability,
i.e., polarization catastrophe, which is the onset of metallization. The locus
of the calculated critical concentrations is in a good agreement with the
experimental phase diagram of Na-NH3 solutions. The proposed mechanism of the
metal-nonmetal transition is quite general and may occur in systems involving
self-trapped quantum quasiparticles.Comment: 13 figures, 42 page
The local phase transitions of the solvent in the neighborhood of a solvophobic polymer at high pressures
We investigate local phase transitions of the solvent in the neighborhood of
a solvophobic polymer chain which is induced by a change of the polymer-solvent
repulsion and the solvent pressure in the bulk solution. We describe the
polymer in solution by the Edwards model, where the conditional partition
function of the polymer chain at a fixed radius of gyration is described by a
mean-field theory. The contributions of the polymer-solvent and the
solvent-solvent interactions to the total free energy are described within the
mean-field approximation. We obtain the total free energy of the solution as a
function of the radius of gyration and the average solvent number density
within the gyration volume. The resulting system of coupled equations is solved
varying the polymer-solvent repulsion strength at high solvent pressure in the
bulk. We show that the coil-globule (globule-coil) transition occurs
accompanied by a local solvent evaporation (condensation) within the gyration
volum
Wavelet treatment of the intra-chain correlation functions of homopolymers in dilute solutions
Discrete wavelets are applied to parametrization of the intra-chain two-point
correlation functions of homopolymers in dilute solutions obtained from Monte
Carlo simulation. Several orthogonal and biorthogonal basis sets have been
investigated for use in the truncated wavelet approximation. Quality of the
approximation has been assessed by calculation of the scaling exponents
obtained from des Cloizeaux ansatz for the correlation functions of
homopolymers with different connectivities in a good solvent. The resulting
exponents are in a better agreement with those from the recent renormalisation
group calculations as compared to the data without the wavelet denoising. We
also discuss how the wavelet treatment improves the quality of data for
correlation functions from simulations of homopolymers at varied solvent
conditions and of heteropolymers.Comment: RevTeX, 19 pages, 7 PS figures. Accepted for publication in PR
Fast calculation of thermodynamic and structural parameters of solutions using the 3DRISM model and the multi-grid method
In the paper a new method to solve the tree-dimensional reference interaction
site model (3DRISM) integral equations is proposed. The algorithm uses the
multi-grid technique which allows to decrease the computational expanses.
3DRISM calculations for aqueous solutions of four compounds (argon, water,
methane, methanol) on the different grids are performed in order to determine a
dependence of the computational error on the parameters of the grid. It is
shown that calculations on the grid with the step 0.05\Angstr and buffer
8\Angstr give the error of solvation free energy calculations less than 0.3
kcal/mol which is comparable to the accuracy of the experimental measurements.
The performance of the algorithm is tested. It is shown that the proposed
algorithm is in average more than 12 times faster than the standard Picard
direct iteration method.Comment: the information in this preprint is not up to date. Since the first
publication of the preprint (9 Nov 2011) the algorithm was modified which
allowed to achieve better results. For the new algorithm see the JCTC paper:
DOI: 10.1021/ct200815v, http://pubs.acs.org/doi/abs/10.1021/ct200815
Density functional study of fluorocarbon emulsions with adsorbed polymer surfactant
Applying density functional treatment based on wavelets, we have investigated the stability of polymer-colloidal solutions in which polymer surfactants can form globules or adsorb at colloidal particles. The results have indicated that the solution becomes unstable due to the aggregation and formation of dimers and trimers when colloidal concentration exceeds the critical one. (c) 2004 Published by Elsevier B.V
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