arXiv subjects

Alina Ciach

Publications and source records attributed to Alina Ciach.

18 recordsLinked to original sources

arXiv2021

Mesoscopic inhomogeneities in concentrated electrolytes

A mesoscopic theory for water-in-salt electrolytes combining density functional and field-theoretic methods is developed in order to explain the unexpectedly large period of the oscillatory decay of the disjoining pressure observed in recent experiments for the LiTFSI (lithium bis(trifluoromethylsulfonyl)-imide) salt [T. S. Groves et. al., J. Phys. Chem. Lett. {\bf 12},1702 (2021)]. We assumed spherical ions with different diameters, and implicit solvent inducing strong, short-range attraction between ions of the same sign. For this highly simplified model, we calculated correlation functions. Our results indicate that mesoscopic inhomogeneities can occur when the sum of the Coulomb and the water-mediated interactions between like ions is attractive at short- and repulsive at large distances. We adjusted the attractive part of the potential to the water-in-LiTFSI electrolyte, and obtained both the period and the decay rate of the correlations in a semiquantitative agreement with the experiment. In particular, the decay length of the correlations increases nearly linearly with the volume fraction of ions.

cond-mat.soft↗

arXiv2020

Effect of proximity to ionic liquid-solvent demixing on electrical double layers

There is a growing interest in the properties of ionic liquids (ILs) and IL-solvent mixtures at metallic interfaces, particularly due to their applications in energy storage. The main focus so far has been on electrical double layers with ILs far from phase transitions. However, the systems in the vicinity of their phase transformations are known to exhibit some remarkable features, such as wetting transitions and capillary condensation. Herein, we develop a mean-field model suitable for the IL-solvent mixtures close to demixing, and combine it with the Carnahan-Starling (CS) and lattice-gas expressions for the excluded volume interactions. This model is then solved analytically, using perturbation expansion, and numerically. We demonstrate that, besides the well-known camel and bell-shaped capacitances, there is a bird-shaped capacitance, having three peaks as a function of voltage, which emerges due to the proximity to demixing. In addition, we find that the camel-shaped capacitance, which is a signature of dilute electrolytes, can appear at high IL densities for ionophobic electrodes. We also discuss the differences and implications arising from the CS and lattice-gas expressions in the context of our model.

cond-mat.soft↗

arXiv2019

Effect of aggregation on adsorption phenomena

Adsorption at an attractive surface in a system with particles self-assembling into small clusters is studied by Molecular dynamics (MD) simulation. We assume Lennard-Jones plus repulsive Yukawa tail interactions, and focus on small densities. The relative increase of the temperature at the critical cluster concentration near the attractive surface (CCCS) shows a power-law dependence on the strength of the wall-particle attraction. At temperatures below the CCCS, the adsorbed layer consists of undeformed clusters if the wall-particle attraction is not too strong. Above the CCCS, or for strong attraction leading to flattening of the adsorbed aggregates, we obtain a monolayer that for strong or very strong attraction consists of flattened clusters or stripes respectively. The accumulated repulsion from the particles adsorbed at the wall leads to a repulsive barrier that slows down the adsorption process, and the accession time grows rapidly with the strength of the wall-particle attraction. Beyond the adsorbed layer of particles, a depletion region of a thickness comparable with the range of the repulsive tail of interactions occurs, and the density in this region decreases with increasing strength of the wall-particle attraction. At larger separations, the exponentially damped oscillations of density agree with theoretical predictions for self-assembling systems. Structural and thermal properties of the bulk are also determined. In particular, a new structural crossover associated with the maximum of the specific heat, and a double-peaked histogram of the cluster size distribution are observed.

cond-mat.stat-mech↗

arXiv2019

Self-Assembly of Spiral Patterns in Confined System with Competing Interactions

Colloidal particles in polymer solutions and functionalized nanoparticles often exhibit short-range attraction coupled with long-range repulsion (SALR) leading to the spontaneous formation of symmetric patterns. Chiral nanostructures formed by thin film of SALR particles have not been reported yet. In this study, we observe striking topological transitions from a symmetric pattern of concentric rings to a chiral structure of a spiral shape, when the system is in hexagonal confinement. We find that the spiral formation can be induced either by breaking the system symmetry with a wedge, or by melting of the rings. In the former case, the chirality of the spiral is determined by orientation of the wedge and thus can be controlled. In the latter, the spiral rises due to thermally induced defects and is absent in the average particle distribution that form highly regular hexagonal patterns in the central part of the system. These hexagonal patterns can be explained by interference of planar density waves. Thermodynamic considerations indicate that equilibrium spirals can appear spontaneously in any stripe-forming system confined in a hexagon with a small wedge, provided that certain conditions are satisfied by a set of phenomenological parameters.

cond-mat.soft↗

arXiv2019

Two-dimensional pattern formation in ionic liquids confined between graphene walls

We perform molecular dynamics simulations of ionic liquids confined between graphene walls under a large variety of conditions (pure ionic liquids, mixtures with water and alcohols, mixtures with lithium salts and defective graphene walls). Our results show that the formation of striped and hexagonal patterns in the Stern layer can be considered as a general feature of ionic liquids at electrochemical interfaces, the transition between patterns being controlled by the net balance of charge in the innermost layer of adsorbed molecules. This explains previously reported experimental and computational results and, for the first time, why these pattern changes are triggered by any perturbation of the charge density at the innermost layer of the electric double layer (voltage and composition changes, and vacancies at the electrode walls, among others), which may help tuning electrode-ionic liquid interfaces. Using Monte Carlo simulations we show that such structures can be reproduced by a simple two-dimensional lattice model with only nearest-neighbour interactions, governed by highly screened ionic interactions and short-range and excluded volume interactions. We also show that the results of our simulations are consistent with those inferred from the Landau-Brazovskii theory of pattern formation in self-assembling systems. The presence of these patterns at the ionic liquid graphene-electrode interfaces may have a strong impact on the process of ionic transfer from the bulk mixtures to the electrodes, on the differential capacitance of the electrode-electrolyte double layer or on the rates of redox reactions at the electrodes, among other physicochemical properties, and is therefore an effect of great technological interest.

cond-mat.soft↗

arXiv2018

Simple theory for oscillatory charge profile in ionic liquids near a charged wall

The mesoscopic field theory for ionic systems [A. Ciach and G. Stell, J. Mol. Liq. 87, 255 (2000)] is extended to the system with charged boundaries. A very simple expression for the excess grand potential functional of the charge density is developed. The size of hard-cores of ions is taken into account in the expression for the internal energy. The functional is suitable for a description of a distribution of ions in ionic liquids and ionic liquid mixtures with neutral components near a weakly charged wall. The Euler-Lagrange equation is obtained, and solved for a flat confining surface. An exponentially damped oscillatory charge density profile is obtained. The electrostatic potential for the restricted primitive model agrees with the simulation results on a semiquantitative level.

cond-mat.soft↗

arXiv2018

Orientational ordering of lamellar structures on closed surfaces

Self-assembly of particles with short-range attraction and long-range repulsion (SALR) interactions on a flat and on a spherical surface is compared. Molecular dynamics (MD) simulations are performed for the two systems having the same area and the density optimal for formation of stripes of particles. Structural characteristics, e.g. a cluster size distribution, a number of defects and an orientational order parameter (OP), as well as the specific heat, are obtained for a range of temperature. In both cases, the cluster size distribution becomes bimodal and elongated clusters appear at the temperature corresponding to the maximum of the specific heat. When the temperature decreases, orientational ordering of the stripes takes place, and the number of particles per cluster or stripe increases in both cases. However, only on the flat surface the specific heat has another maximum at the temperature corresponding to a rapid change of the OP. On the sphere, the crossover between the isotropic and anisotropic structures occurs in a much broader temperature interval, the orientational order is weaker, and occurs at significantly lower temperature. At low temperature the stripes on the sphere form spirals, and the defects resemble defects in the nematic phase of rods adsorbed at a sphere.

cond-mat.soft↗

arXiv2016

Exactly solvable model for self-assembly of hard core - soft shell particles at interfaces

A lattice model with soft repulsion followed by attraction is developed for a monolayer of hybrid core-shell particles self-assembling at an interface. The model is solved exactly in one dimension. One, two or three periodic structures and variety of shapes of the pressure-density isotherms may occur in different versions of the model. For strong interactions the isotherm consists of vertical segments separated by plateaus. The range of order depends strongly on the strength of attraction and on the density. Our results agree with experimental observations.

cond-mat.soft↗

arXiv2016

Self-consistent theory for inhomogeneous systems with mesoscopic fluctuations

We have developed a theory for inhomogeneous systems that allows for incorporation of effects of mesoscopic fluctuations. A hierarchy of equations relating the correlation and direct correlation functions for the local excess $ϕ({\bf r})$ of the volume fraction of particles $ζ$ has been obtained, and an approximation leading to a closed set of equations for the two-point functions has been introduced. We have solved numerically the self-consistent equations for one (1D) and three (3D) dimensional models with short-range attraction and long-rannge repulsion (SALR). Predictions for all the qualitative properties of the 1D model agree with the exact results, but only semi-quantitative agreement is obtained in the simplest version of the theory. The effects of fluctuations in the two considered 3D models are significantly different, despite very similar properties of these models in the mean-field approximation. In both cases we obtain the sequence of large - small - large compressibility for increasing $ζ$. The very small compressibility is accompanied by the oscillatory decay of correlations with the correlation length orders of magnitude larger than the size of particles. Only in one of the two considered models for decreasing temperature the small compressibility becomes very small and the large compressibility becomes very large, and eventually van der Waals loops appear. Further studies are necessary to determine the nature of the strongly inhomogeneous phase present for intermediate volume fractions in 3D.

cond-mat.stat-mech↗

arXiv2014

Bistability in a self-assembling system confined by elastic walls. Exact results in a one-dimensional lattice model

The impact of confinement on self-assembly of particles interacting with short-range attraction and long-range repulsion (SALR) potential is studied for thermodynamic states corresponding to local ordering of clusters or layers in the bulk. Exact and asymptotic expressions for the local density and for the effective potential between the confining surfaces are obtained for a one-dimensional lattice model introduced in [J. Pękalski et al. $J. Chem. Phys.$ ${\bf 140}$, 144903 (2013)].The simple asymptotic formulas are shown to be in good quantitative agreement with exact results for slits containing at least 5 layers. We observe that the incommensurability of the system size and the average distance between the clusters or layers in the bulk leads to structural deformations that are different for different values of the chemical potential $μ$. The change of the type of defects is reflected in the dependence of density on $μ$ that has a shape characteristic for phase transitions. Our results may help to avoid misinterpretation of the change of the type of defects as a phase transition in simulations of inhomogeneous systems. Finally, we show that a system confined by soft elastic walls may exhibit bistability such that two system sizes that differ approximately by the average distance between the clusters or layers are almost equally probable. This may happen when the equilibrium separation between the soft boundaries of an empty slit corresponds to the largest stress in the confined self-assembling system.

cond-mat.soft↗

arXiv2014

Self-assembly of lipids in water. Exact results from a one-dimensional lattice model

We consider a lattice model for amphiphiles in a solvent with molecules chemically similar to one part of the amphiphilic molecule. The dependence of the interaction potential on orientation of the amphiphilic molecules is taken into account explicitly. The model is solved exactly in one dimension by the transfer-matrix method. In particular, pressure as a function of concentration, correlation function and specific heat are calculated. The model is compared with the recently introduced lattice model for colloidal self-assembly, where the particles interact with the isotropic short-range attraction and long-range repulsion (SALR) potential. Similarities between the amphiphilic and the colloidal self-assembly are highlighted.

cond-mat.soft↗

arXiv2014

Simple one-dimensional lattice model for lipids in water

A lattice model for binary mixture of lipids and water is introduced and investigated. The orientational degrees of freedom of the amphiphilic molecules are taken into account in the same way as in the model for oil-water-surfactant mixtures introduced earlier by Johan Høye and co-authors. The ground state of the model is discussed in detail, and the mean-field stability analysis of the disordered phase is performed. The model is compared to the recently introduced lattice model for colloidal self-assembly.

cond-mat.soft↗

arXiv2014

Effect of antagonistic salt on confined near-critical mixture

We consider a near-critical binary mixture with addition of antagonistic salt confined between weakly charged and selective surfaces. A mesoscopic functional for this system is developed from a microscopic description by a systematic coarse-graining procedure. The functional reduces to the Landau-Brazovskii functional for amphiphilic systems for sufficiently large ratio between the correlation length in the critical binary mixture and the screening length. Our theoretical result agrees with the experimental observation [Sadakane et.al. J. Chem. Phys. {\bf 139}, 234905 (2013)] that the antagonistic salt and surfactant both lead to a similar mesoscopic structure. For very small salt concentration $ρ_{ion}$ the Casimir potential is the same as in a presence of inorganic salt. For larger $ρ_{ion}$ the Casimir potential takes a minimum followed by a maximum for separations of order of tens of nanometers, and exhibits an oscillatory decay very close to the critical point. For separations of tens of nanometers the potential between surfaces with a linear size of hundreds of nanometers can be of order of $k_BT$. We have verified that in the experimentally studied samples [Sadakane et.al. J. Chem. Phys. {\bf 139}, 234905 (2013), Leys et.al. Soft Matter {\bf 9}, 9326 (2013)] the decay length is too small compared to the period of oscillations of the Casimir potential, but the oscillatory force could be observed closer to the critical point.

cond-mat.soft↗

arXiv2013

How ions in solution can change the sign of the critical Casimir potential

We show that hydrophilic ions present in a confined, near-critical aqueous mixture can lead to an attraction between like charge surfaces with opposing preferential adsorption of the two species of the mixture, even though the corresponding Casimir potential in uncharged systems is repulsive. This prediction agrees with recent experiment [Nellen {\it{et al.}}, Soft Matter{\bf{80}}, 061143 (2011)]. We also show that oppositely charged hydrophobic surfaces can repel each other, although the Casimir potential between uncharged surfaces with like preferential adsorption (selectivity) is attractive. This behavior is expected when the electrostatic screening length is larger than the correlation length, and one of the confining surfaces is strongly selective and weakly charged, whereas the other confining surface is weakly selective and strongly charged. The Casimir potential can change sign because the hydrophilic ions near the weakly hydrophobic surface can overcompensate the effect of hydrophobicity, and this surface can act as a hydrophilic one. We also predict a more attractive interaction between hydrophilic surfaces and a more repulsive interaction between hydrophobic surfaces than given by the sum of the Casimir and Deby-Hückel potentials. Our theory is derived systematically from a microscopic approach, and combines the Landau-type and Debye-Hückel theories with an additional contribution of an entropic origin.

cond-mat.soft↗

arXiv2012

Effect of mesoscopic fluctuations on equation of state in cluster-forming systems

Equation of state for systems with particles self-assembling into aggregates is derived within a mesoscopic theory combining density functional and field-theoretic approaches. We focus on the effect of mesoscopic fluctuations in the disordered phase. The pressure -- volume fraction isotherms are calculated explicitly for two forms of the short-range attraction long-range repulsion potential. Mesoscopic fluctuations lead to an increased pressure in each case, except for very small volume fractions. When large clusters are formed, the mechanical instability of the system is present at much higher temperature than found in mean-field approximation. In this case phase separation competes with the formation of periodic phases (colloidal crystals). In the case of small clusters, no mechanical instability associated with separation into dilute and dense phases appears.

cond-mat.stat-mech↗

arXiv2012

Effect of ions on confined near-critical binary aqueous mixture

Near-critical binary mixtures containing ions and confined between two charged and selective surfaces are studied within a Landau-Ginzburg theory extended to include electrostatic interactions. Charge density profiles and the effective interactions between the confining surfaces are calculated in the case of chemical preference of ions for one of the solvent components. Close to the consolute point of the binary solvent, the preferential solubility of ions leads to the modification of the charge density profiles in respect to the ones obtained from the Debye-Hückel theory. As a result, the electrostatic contribution to the effective potential between the charged surface can exhibit an attractive well. Our calculations are based on the approximation scheme valid if the bulk correlation length of a solvent is much larger than the Debye screening length; in this critical regime the effect of charge on the concentration profiles of the solvent is subdominant. Such conditions are met in the recent measurements of the effective forces acting between a substrate and a spherical colloidal particle immersed in the near-critical water-lutidine mixture [Nature V. 451, 172 (2008)]. Our analytical results are in a quantitative agreement with the experimental ones.

cond-mat.soft↗

arXiv2010

Distribution of ions near a charged selective surface in critical binary solvents

Near-critical binary mixtures containing ionic solutes near a charged wall preferentially adsorbing one component of the solvent are studied. Within the Landau-Ginzburg approach extended to include electrostatic interactions and the chemical preference of ions for one component of the solvent, we obtain a simple form for the leading-order correction to the Debye-Huckel theory result for the charge density profile. Our result shows that critical adsorption influences significantly distribution of ions near the wall. This effect may have important implications for the screening of electrostatic interactions between charged surfaces immersed in binary near-critical solvents.

cond-mat.stat-mech↗

arXiv2006

Universality class of the critical point in the restricted primitive model of ionic systems

A coarse-grained description of the restricted primitive model is considered in terms of the local charge- and number-density fields. Exact reduction to a one-field theory is derived, and exact expressions for the number-density correlation functions in terms of higher-order correlation functions for the charge-density are given. It is shown that in continuum space the singularity of the charge-density correlation function associated with short-wavelength charge-ordering disappears when charge-density fluctuations are included by following the Brazovskii approach. The related singularity of the individual Feynman diagrams contributing to the number-density correlation functions is cured when all the diagrams are segregated ito disjoint sets according to their topological structure. By performing a resummation of all diagrams belonging to each set a regular expression represented by a secondary diagram is obtained. The secondary diagrams are again segregated into disjoint sets, and the series of all the secondary diagrams belonging to a given set is represented by a hyperdiagram. A one-to-one correspondence between the hyperdiagrams contributing to the number-density vertex functions, and diagrams contributing to the order-parameter vertex functions in a certain model system belonging to the Ising universality class is demonstrated. Corrections to scaling associated with irrelevant operators that are present in the model-system Hamiltonian, and other corrections specific to the RPM are also discussed.

cond-mat.stat-mech↗