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Nikolai N. Kalikin

Publications and source records attributed to Nikolai N. Kalikin.

5 recordsLinked to original sources

Stress Tensor in Fundamental Measure Theory of Hard-Sphere Fluids: A Thermomechanical Approach

We derive the local pressure tensor generated by the original Rosenfeld fundamental measure theory (FMT) for hard-sphere fluids from an arbitrary infinitesimal deformation. The variation of a finite-distance FMT kernel is written via the line integrals of the local deformation gradient along the straight segment connecting its endpoints. The resulting symmetric pressure tensor consists of a local term expressed through the standard FMT weighted densities and a finite-range chord term. For a monodisperse hard-sphere fluid, differential relations between the Rosenfeld measures reduce the tensor to a closed one-body form. We demonstrate that no independent pair density or inhomogeneous Ornstein--Zernike equation is required. In the limit of homogeneous fluid the tensor reproduces the Percus--Yevick compressibility equation of state. In planar confinement the normal stress satisfies the hard-wall contact relation, the mechanical surface tension agrees with the surface excess grand potential, and the disjoining pressure agrees with the derivative of the confined grand potential with respect to slit width. The finite-range chord term extends the deformation method from local field theories to nonlocal weighted-density functionals.

cond-mat.soft↗

A Fluctuation Theory of Liquid-Phase Solutions: Shear Viscosity

Accurately describing liquids and their mixtures beyond equilibrium remains a significant challenge in modern chemical physics and physical chemistry, especially regarding the calculation of transport properties in liquid-phase systems. This paper introduces a phenomenological nonequilibrium theory specifically designed for multicomponent liquid-phase solutions. Our field-theoretical framework, rooted in nonequilibrium statistical mechanics, incorporates quasi-stationary concentration fluctuations that align with equilibrium liquid theory as described by classical density functional theory. This method serves as a phenomenological extension of the established Dean-Kawasaki stochastic density functional theory, enabling the computation of shear viscosity. We apply our approach to derive general formula for the shear viscosity in single-solute solutions. Our findings yield new results and successfully reproduce previously established results for such systems as solutions containing soft-core particles, hard spheres, one-component plasma, and near-critical solutions.

cond-mat.soft↗

Surface Tension of Aqueous Electrolyte Solutions. A Thermomechanical Approach

We determine the surface tension of aqueous electrolyte solutions in contact with non-polar dielectric media using a thermomechanical approach, which involves deriving the stress tensor from the thermodynamic potential of an inhomogeneous fluid. To obtain the surface tension, we calculate both the normal and tangential pressures using the components of the stress tensor, recently derived by us [Y. A. Budkov and P. E. Brandyshev, The Journal of Chemical Physics 159 (2023)] within the framework of Wang's variational field theory. Using this approach, we derive an analytical expression for the surface tension in the linear approximation. At low ionic concentrations, this expression represents the classical Onsager-Samaras limiting law. By utilizing only one fitting parameter, which is related to the affinity of anions to the dielectric boundary, we can approximate various experimental data regarding the surface tension of aqueous electrolyte solutions. This approximation applies to both the solution-air and solution-dodecane interfaces, covering a wide range of electrolyte concentrations.

cond-mat.soft↗

Electrochemistry meets polymer physics: polymerized ionic liquids on an electrified electrode

Polymeric ionic liquids are emerging polyelectrolyte materials for modern electrochemical applications. In this paper, we propose a self-consistent field theory of the polymeric ionic liquid on a charged conductive electrode. Taking into account the conformation entropy of rather long polymerized cations within the Lifshitz theory and electrostatic and excluded volume interactions of ionic species within the mean-field approximation, we obtain a system of self-consistent field equations for the local electrostatic potential and average concentrations of monomeric units and counterions. We solve these equations in the linear approximation for the cases of a point-like charge and a flat infinite uniformly charged electrode immersed in a polymeric ionic liquid and derive analytical expressions for local ionic concentrations and electrostatic potential, and derive an analytical expression for the linear differential capacitance of the electric double layer. We also find a numerical solution to the self-consistent field equations for two types of boundary conditions for the local polymer concentration on the electrode, corresponding to the cases of the specific adsorption absence (indifferent surface) and strong short-range repulsion of the monomeric units near the charged surface (hard wall case). For both cases, we investigate the behavior of differential capacitance as a function of applied voltage for a pure polymeric ionic liquid and a polymeric ionic liquid dissolved in a polar organic solvent. We observe that the differential capacitance profile shape is strongly sensitive to the adopted boundary condition for the local polymer concentration on the electrode.

cond-mat.soft↗

Molecular theory of electrostatic collapse of dipolar polymer gels

We develop a new quantitative molecular theory of liquid-phase dipolar polymer gels. We model monomer units of the polymer network as a couple of charged sites separated by a fluctuating distance. For the first time, within the random phase approximation, we have obtained an analytical expression for the electrostatic free energy of the dipolar gel. Depending on the coupling parameter of dipole-dipole interactions and the ratio of the dipole length to the subchain Kuhn length, we describe the gel collapse induced by electrostatic interactions in the good solvent regime as a first-order phase transition. This transition can be realized at reasonable physical parameters of the system (temperature, solvent dielectric constant, and dipole moment of monomer units). The obtained results could be potentially used in modern applications of stimuli-responsive polymer gels and microgels, such as drug delivery, nanoreactors, molecular uptake, coatings, superabsorbents, etc.

cond-mat.soft↗