414 research outputs found
McMillan–Mayer theory for solvent effects in inhomogeneous systems: Calculation of interaction pressure in aqueous electrical double layers
We demonstrate how to use the McMillan–Mayer theory to include solvent effects in effective solute–solute interactions for inhomogeneous systems, extending a recent derivation [S. Marčelja, Langmuir 16, 6081 (2000)] for symmetric planar double layers to the general case. In the exact treatment, the many-body potential of mean force between the solute molecules can be evaluated for an inhomogeneous reference system in equilibrium with pure bulk solvent. The reference system contains only solvent and a finite number, n, of fixed solute molecules and it has an external potential that in some cases is different from that of the original system. It is discussed how the n-body potential of mean force between the ions for the relevant cases of large n values can be approximated by a sum of effective singlet and pair interactions evaluated in the presence of, on average, all n ions, i.e., at finite concentration. In examples considered in this work we use effective interionic pair potentials evaluated from bulk electrolyte calculations at finite electrolyte concentrations. We calculate the contribution to the double layer interaction pressure arising from the interaction between ions dissolved in aqueous electrolyte. In cases of moderate or high surface charge, calculations show several new effects. At small surface separations one finds attractive and then strongly repulsive contributions. For surface charge density around one negative charge per 70 Å2 the full results for pressures resemble “secondary hydration force” measured in classical experiments in 1980s. When there is a tendency for ions to adsorb at the surfaces there is a marked change in behavior. The force is then oscillatory, reminiscent of results obtained with the surface force apparatus at low electrolyte concentration
Effective solvent mediated potentials of Na+ and Cl− ions in aqueous solution: temperature dependence
How would you integrate the equations of motion in dissipative particle dynamics simulations?
In this work we assess the quality and performance of several novel
dissipative particle dynamics integration schemes that have not previously been
tested independently. Based on a thorough comparison we identify the respective
methods of Lowe and Shardlow as particularly promising candidates for future
studies of large-scale properties of soft matter systems
On the nature of long-range contributions to pair interactions between charged colloids in two dimensions
We perform a detailed analysis of solutions of the inverse problem applied to
experimentally measured two-dimensional radial distribution functions for
highly charged latex dispersions. The experiments are carried out at high
colloidal densities and under low-salt conditions. At the highest studied
densities, the extracted effective pair potentials contain long-range
attractive part. At the same time, we find that for the best distribution
functions available the range of stability of the solutions is limited by the
nearest neighbour distance between the colloidal particles. Moreover, the
measured pair distribution functions can be explained by purely repulsive pair
potentials contained in the stable part of the solution.Comment: 6 pages, 5 figure
Coupled coarse graining and Markov Chain Monte Carlo for lattice systems
We propose an efficient Markov Chain Monte Carlo method for sampling
equilibrium distributions for stochastic lattice models, capable of handling
correctly long and short-range particle interactions. The proposed method is a
Metropolis-type algorithm with the proposal probability transition matrix based
on the coarse-grained approximating measures introduced in a series of works of
M. Katsoulakis, A. Majda, D. Vlachos and P. Plechac, L. Rey-Bellet and
D.Tsagkarogiannis,. We prove that the proposed algorithm reduces the
computational cost due to energy differences and has comparable mixing
properties with the classical microscopic Metropolis algorithm, controlled by
the level of coarsening and reconstruction procedure. The properties and
effectiveness of the algorithm are demonstrated with an exactly solvable
example of a one dimensional Ising-type model, comparing efficiency of the
single spin-flip Metropolis dynamics and the proposed coupled Metropolis
algorithm.Comment: 20 pages, 4 figure
Monte Carlo simulation and global optimization without parameters
We propose a new ensemble for Monte Carlo simulations, in which each state is
assigned a statistical weight , where is the number of states with
smaller or equal energy. This ensemble has robust ergodicity properties and
gives significant weight to the ground state, making it effective for hard
optimization problems. It can be used to find free energies at all temperatures
and picks up aspects of critical behaviour (if present) without any parameter
tuning. We test it on the travelling salesperson problem, the Edwards-Anderson
spin glass and the triangular antiferromagnet.Comment: 10 pages with 3 Postscript figures, to appear in Phys. Rev. Lett
Hydration interactions: aqueous solvent effects in electric double layers
A model for ionic solutions with an attractive short-range pair interaction
between the ions is presented. The short-range interaction is accounted for by
adding a quadratic non-local term to the Poisson-Boltzmann free energy. The
model is used to study solvent effects in a planar electric double layer. The
counter-ion density is found to increase near the charged surface, as compared
with the Poisson-Boltzmann theory, and to decrease at larger distances. The ion
density profile is studied analytically in the case where the ion distribution
near the plate is dominated only by counter-ions. Further away from the plate
the density distribution can be described using a Poisson-Boltzmann theory with
an effective surface charge that is smaller than the actual one.Comment: 11 Figures in 13 files + LaTex file. 20 pages. Accepted to Phys. Rev.
E. Corrected typos and reference
Attractive Interactions Between Rod-like Polyelectrolytes: Polarization, Crystallization, and Packing
We study the attractive interactions between rod-like charged polymers in
solution that appear in the presence of multi-valence counterions. The
counterions condensed to the rods exhibit both a strong transversal
polarization and a longitudinal crystalline arrangement. At short distances
between the rods, the fraction of condensed counterions increases, and the
majority of these occupy the region between the rods, where they minimize their
repulsive interactions by arranging themselves into packing structures. The
attractive interaction is strongest for multivalent counterions. Our model
takes into account the hard-core volume of the condensed counterions and their
angular distribution around the rods. The hard core constraint strongly
suppresses longitudinal charge fluctuations.Comment: 4 figures, uses revtex, psfig and epsf. The new version contains a
different introduction, and the bibliography has been expande
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