89 research outputs found
Unraveling the behavior of the individual ionic activity coefficients on the basis of the balance of ion-ion and ion-water interactions
We investigate the individual activity coefficients of pure 1:1 and 2:1
electrolytes using our theory that is based on the competition of ion-ion (II)
and ion-water (IW) interactions (Vincze et al., J. Chem. Phys. 133, 154507,
2010). The II term is computed from Grand Canonical Monte Carlo simulations on
the basis of the implicit solvent model of electrolytes using hard sphere ions
with Pauling radii. The IW term is computed on the basis of Born's treatment of
solvation using experimental hydration free energies. The two terms are coupled
through the concentration-dependent dielectric constant of the electrolyte.
With this approach we are able to reproduce the nonmonotonic concentration
dependence of the mean activity coefficient of pure electrolytes qualitatively
without using adjustable parameters. In this paper, we show that the theory can
provide valuable insight into the behavior of individual activity coefficients
too. We compare our theoretical predictions against experimental data measured
by electrochemical cells containing ion-specific electrodes. As in the case of
the mean activity coefficients, we find good agreement for 2:1 electrolytes,
while the accuracy of our model is worse for 1:1 systems. This deviation in
accuracy is explained by the fact that the two competing terms (II and IW) are
much larger in the 2:1 case so errors in the two separate terms have less
effects. The difference of the excess chemical potentials of cations and anions
(the ratio of activity coefficients) is determined by asymmetries in the
properties of the two ions: charge, radius, and hydration free energies.Comment: 32 pages, 8 figures, 1 TOC figur
The effect of the charge pattern on the applicability of a nanopore as a sensor
We investigate a model nanopore sensor that is able to detect analyte ions
that are present in the electrolyte solution in very small concentrations. The
nanopore selectively binds the analyte ions with which the local concentrations
of the ions of the background electrolyte (KCl), and, thus, the ionic current
flowing through the pore is changed. Analyte concentration can be determined
from calibration curves. In our previous study (M\'{a}dai et al. J. Chem.
Phys., 147(24):244702, 2017.), we proposed a symmetric model (surface charge is
negative all along the pore). The mechanism of sensing was a competition
between K and positive analyte ions, so increasing analyte concentration
decreased K current. Here we allow asymmetric charge patterns on the pore
wall (positive/negative/neutral along the pore), thus, gaining an additional
device function, rectification, resulting in a dual responsive device. We find
that a bipolar nanopore is an efficient geometry with Cl ions being the
main charge carriers. The mechanism of sensing is that more positive analyte
ions attract more Cl ions into the pore thus increasing the current. Also
they make the pore less asymmetric and, thus, decrease rectification. We use a
hybrid computer simulation method, where a generalization of the grand
canonical Monte Carlo method to non-equilibrium (Local Equilibrium Monte Carlo)
is coupled to the Nernst-Planck equation with which the flux is computed
Comment on “The Role of Concentration Dependent Static Permittivity of Electrolyte Solutions in the Debye–Hückel Theory”
Comment on “The Role of Concentration Dependent
Static Permittivity of Electrolyte Solutions in the Debye–Hückel
Theory
The effect of concentration- and temperature-dependent dielectric constant ont the activity coefficient of NaCl electrolyte solutions
Our implicit-solvent model for the estimation of the excess chemical potential (or, equivalently, the activity coefficient) of electrolytes is based on using a dielectric constant that depends on the thermodynamic state, namely, the temperature and concentration of the electrolyte, ε(c, T). As a consequence, the excess chemical potential is split into two terms corresponding to ion-ion (II) and ion-water (IW) interactions. The II term is obtained from computer simulation using the Primitive Model of electrolytes, while the IW term is estimated from the Born treatment. In our previous work [J. Vincze, M. Valiskó, and D. Boda, "The nonmonotonic concentration dependence of the mean activity coefficient of electrolytes is a result of a balance between solvation and ion-ion correlations," J. Chem. Phys. 133, 154507 (2010)], we showed that the nonmonotonic concentration dependence of the activity coefficient can be reproduced qualitatively with this II+IW model without using any adjustable parameter. The Pauling radii were used in the calculation of the II term, while experimental solvation free energies were used in the calculation of the IW term. In this work, we analyze the effect of the parameters (dielectric constant, ionic radii, solvation free energy) on the concentration and temperature dependence of the mean activity coefficient of NaCl. We conclude that the II+IW model can explain the experimental behavior using a concentration-dependent dielectric constant and that we do not need the artificial concept of "solvated ionic radius" assumed by earlier studies
Activity coefficients of individual ions in LaCl3 from the II+IW theory
We investigate the individual activity coefficients of ions in LaCl3 using our theory that is based on the competition of ion–ion (II) and ion–water (IW) interactions. The II term is computed from Grand Canonical Monte Carlo simulations on the basis of the implicit solvent model of electrolytes using hard sphere ions with Pauling radii. The IW term is computed on the basis of Born's treatment of solvation using experimental hydration-free energies. The results show good agreement with experimental data for La3+. This agreement is remarkable considering the facts that (i) the result is the balance of two terms that are large in absolute value (up to 20 kT) but opposite in sign, and (ii) that our model does not contain any adjustable parameter. All the parameters used in the model are taken from experiments: concentration-dependent dielectric constant, hydration free energies and Pauling radii
Controlling ion transport through nanopores: modeling transistor behavior
We present a modeling study of a nanopore-based transistor computed by a
mean-field continuum theory (Poisson-Nernst-Planck, PNP) and a hybrid method
including particle simulation (Local Equilibrium Monte Carlo, LEMC) that is
able to take ionic correlations into account including finite size of ions. The
model is composed of three regions along the pore axis with the left and right
regions determining the ionic species that is the main charge carrier, and the
central region tuning the concentration of that species and, thus, the current
flowing through the nanopore. We consider a model of small dimensions with the
pore radius comparable to the Debye-screening length
(), which, together with large
surface charges provides a mechanism for creating depletion zones and, thus,
controlling ionic current through the device. We report scaling behavior of the
device as a function the parameter.
Qualitative agreement between PNP and LEMC results indicates that mean-field
electrostatic effects determine device behavior to the first order
Ionos és poláros molekuláris rendszerek szimulációs vizsgálata dielektromos határfelületek jelenlétében Dirichlet-féle peremfeltétel alkalmazásával = Simulation study of ionic and polar molecular systems in the presence of dielectric boundaries applying Dirichlet boundary condition
Metodikai fejlesztéseink során a dielektromos határfelületek korrekt kezelésén, a Poisson-egyenlet megfelelő peremfeltételek mellett való megoldásán, és a nagykanonikus Monte Carlo szimulácók hatékony használatán alapulva olyan programokat fejlesztettünk ki, amelyek segítségével lehetővé vált különböző problémák szimulációs vizsgálata. Jelentős eredményeket értünk el kalcium- és nátriumcsatornák valamint nanopórusok szelektivitási mechanizmusainak megértése terén és a kísérletekkel egyező eredményeket kaptunk. A Nernst-Planck egyenlet integrálásával egy módszert javasoltunk Monte Carlo szimulációs eredményeink és a kísérletek által szolgáltatott vezetőképességi adatok összevetésére. Az elekrokémiai kettősrétegek esetében megvizsgáltuk erősen töltött elektródok szelektív adszorpciójának energetikáját. Adszorpciós vizsgálataink olyan gyakorlati szempontból is fontos rendszerekre terjedtek ki, mint egy HIV fehérje, valamint különböző vendégmolekulák interkalációja zeolitokban és kaolinitben. A pályázat során produkált publikációs összes impakt faktora 68,31, a rájuk kapott független hivatkozások száma 71. | Methodological developments - including correct treatment of dielectric boundaries, solution of the Poisson equation using appropriate boundary conditions, and efficient application of the grand canonical Monte Carlo technique - made it possible to study various practical problems with simulations. We obtained important results for selectivity mechanisms of calcium and sodium channels as well as nanopores. We obtained results that are in agreement with experiments. We suggested a method - based on the integration of the Nernst-Planck equation - with which we can relate our Monte Carlo results to experimental conductance data. In the case of the electrochemical double layers we studied the energetics of the selectivity of highly charged electrodes. Our adsorption studies included such practically important systems as a HIV protein and intercalation of various guest molecules in zeolites and kaolinite. Our papers published with the help of the grant have a total impact factor 68.31 and obtained 71 independent citations
The origin of the interparticle potential of electrorheological fluids
The particles of electrorheological fluids can be modelled a
s dielectric sphere (DS) immersed in a continuum dielectric. When an external field is applied, polarization
charges are induced on the surfaces of the spheres that can be represented as point dipoles placed in the centres of the spheres. When the DSs are close to each other, the induced charge distributions are distorted by the electric field of the neighbouring DSs. This is the origin of the interaction potential between the DSs. The calculation of this energy is very time consuming, therefore, the DS model cannot be used in molecular simulations. In this paper, we show that the interaction between the point dipoles approximates the interaction of DSs appropriately. The polarizable point dipole model provides better results, but this model is not pair-wise additive, so it is not so practical in particle simulations
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