Macroscopic forces in inhomogeneous polyelectrolyte solutions
Physical Review E - Statistical, Nonlinear, and Soft Matter Physics. 2023. Vol. 107. No. 2. Article 024503.
Budkov Y., Kalikin N.
In this paper, we present a self-consistent field theory of macroscopic forces in spatially inhomogeneous flexible chain polyelectrolyte solutions. We derive an analytical expression for a stress tensor which consists of three terms: isotropic hydrostatic stress, electrostatic (Maxwell) stress, and stress rising from conformational entropy of polymer chains—conformational stress. We apply our theory to the description of polyelectrolyte solutions confined in a conductive slit nanopore and observe anomalous behavior of disjoining pressure and electric differential capacitance.
Research target: Physics Chemistry Nanotechnologies
, , Journal of Statistical Mechanics: Theory and Experiment 2022 Vol. 2022 Article 053205
We propose a field-theoretical approach based on the thermodynamic perturbation theory and within it derive a grand thermodynamic potential of the inhomogeneous ionic fluid as a functional of electrostatic potential for an arbitrary reference fluid system. We obtain a modified Poisson–Boltzmann (PB) equation as the Euler–Lagrange equation for the obtained functional. Applying Noether's theorem to ...
Added: May 12, 2022
Two-component Electrolyte Solutions with Dipolar Cations on a Charged Electrode: Theory and Computer Simulations
, , et al., Journal of Physical Chemistry C 2020 Vol. 124 No. 30 P. 16308-16314
The development of advanced electrochemical devices for energy conversion and storage requires fine tuning of electrode reactions, which can be accomplished by altering the electrode/solution interface structure. Particularly, in case of an alkali-salt electrolyte the electric double layer (EDL) composition can be managed by introducing organic cations (e.g. room temperature ionic liquid cations) that may ...
Added: July 2, 2020
Effects of Enhanced Flexibility and Pore Size Distribution on Adsorption-Induced Deformation of Mesoporous Materials
, , et al., Langmuir 2018 Vol. 34 No. 25 P. 7575-7584
Here, we present a new model of adsorption-induced deformation of mesoporous solids. The model is based on a simplified version of local density functional theory in the framework of solvation free energy. Instead of density, which is treated as constant here, we used film thickness and pore radius as order parameters. This allows us to ...
Added: July 1, 2018
Disjoining pressure of room temperature ionic liquid in charged slit carbon nanopore: molecular dynamics study
, , et al., Journal of Molecular Liquids 2022 Vol. 366 Article 120307
We present a study of the behavior of the room-temperature ionic liquid (1-ethyl-3-methylimidazolium tetrafluoroborate) in negatively charged carbon slit nanopores of various widths (1÷15 nm) using all-atom and coarse-grained molecular dynamics simulations. For the room temperature ionic liquids, we calculate and analyze the disjoining pressure as a function of pore width from the all-atom and ...
Added: September 17, 2022
, , , Journal of Physical Chemistry C 2021 Vol. 125 No. 38 P. 21151-21159
We formulate a general mean-field theory for a flat electric double layer in ionic liquids and electrolyte solutions with ions possessing static polarizability and a permanent dipole moment on a charged electrode. We establish a new analytical expression for electric double-layer differential capacitance, determining it as an absolute value of the ratio of the local ...
Added: September 16, 2021
, , , Physical Chemistry Chemical Physics 2022 Vol. 24 P. 1355-1366
Polymeric ionic liquids are emerging polyelectrolyte materials for modern electrochemical applications. In this paper, we propose a self-consistent field theory of a polymeric ionic liquid on a charged conductive electrode. Taking into account the conformational entropy of rather long polymerized cations within the Lifshitz theory and electrostatic and excluded volume interactions of ionic species within ...
Added: December 26, 2021
Correction: Electrochemistry meets polymer physics: polymerized ionic liquids on an electrified electrode
, , , Physical Chemistry Chemical Physics 2022 Vol. 24 P. 2665-2665
Correction for ‘Electrochemistry meets polymer physics: polymerized ionic liquids on an electrified electrode’ by Yury A. Budkov et al., Phys. Chem. Chem. Phys., 2022, DOI: 10.1039/d1cp04221a. ...
Added: April 6, 2023
Electric double layer theory for room temperature ionic liquids on charged electrodes: milestones and prospects
, , Current Opinion in Electrochemistry 2022 Vol. 33 Article 100931
In this review, we shortly summarize the basic theoretical milestones achieved in the mean-field theory of room temperature ionic liquids (RTILs) on charged electrodes since the publication of Kornyshev’s seminal paper in 2007. We pay special attention to the behavior of the differential capacitance profile and the microscopic parameters of ions that can have substantial ...
Added: January 5, 2022
, , et al., Electrochimica Acta 2018 Vol. 284 P. 346-354
We propose and develop a classical density functional theory for the description of a minor amount of water dissolved in ionic liquid in the vicinity of an electrode. In addition to the electrostatic energy and lattice-gas mixing entropy terms, the utilised grand canonical potential contains several phenomenological terms/parameters that describe short-range interactions between ions of ...
Added: August 3, 2018
A molecular insight into poly(methyl methacrylate) impregnation with mefenamic acid in supercritical carbon dioxide: A computational simulation
, , , Journal of Molecular Liquids 2021 Vol. 337 Article 116424
The process of poly(methyl methacrylate) (PMMA) matrix impregnation with mefenamic acid (MFA) in a supercritical carbon dioxide medium has been studied by the full atomistic classical molecular dynamics method. Simulations have been performed for two systems that differ in the polymer sample size (≈270 kDa and ≈1080 kDa) at 333 K and 40 MPa. The characteristics of the systems, ...
Added: May 10, 2021
АНАЛИЗ УСЛОВИЙ ЭЛЕКТРОЛИТИЧЕСКОГО ФОРМИРОВАНИЯ АНСАМБЛЕЙ МЕТАЛЛИЧЕСКИХ НАНОПРОВОЛОК В ПОРАХ ТРЕКОВЫХ МЕМБРАН
, , et al., Теоретические основы химической технологии 2021 Т. 55 № 4 С. 632-641
The role of the electrolyte composition, mass transfer conditions, pore diameter, distance between them and electrical parameters on the formation of an ensemble of nanowires during the electrodeposition of individual metals and alloys into the pores of polymer films, as well as during the alternation of layers of alloys of different chemical composition, is considered and analyzed. Based ...
Added: November 12, 2021
, , et al., ACS Applied Materials & Interfaces 2020 Vol. 12 No. 49 P. 55141-55147
We propose a novel strategy to enhance optoelectrical properties of single-walled carbon nanotube (SWCNT) films for transparent electrode applications by film patterning. First, we theoretically considered the effect of the conducting pattern geometry on the film quality factor and then experimentally examined the calculated structures. We extend these results to show that the best characteristics ...
Added: November 30, 2020
, Journal of Physics: Condensed Matter 2020 Vol. 32 No. 5 P. 055101-1-055101-8
In this paper, we formulate a field-theoretical model of dilute salt solutions of electrically neutral spherical colloid particles. Each colloid particle consists of a 'central' charge that is situated at the center and compensating peripheral charges (grafted to it) that are fixed or fluctuating relative to the central charge. In the framework of the random ...
Added: October 12, 2019
Molecular Dynamics Study of the Swelling of Poly(methyl methacrylate) in Supercritical Carbon Dioxide
, , , Materials 2019 Vol. 12 No. 20 P. 3315
The swelling of a poly (methyl methacrylate) in supercritical carbon dioxide was studied by means of full atomistic classical molecular dynamics simulation. In order to characterize the polymer swelling, we calculated various properties related to the density, structure, and dynamics of polymer chains as a function of the simulation time, temperature, and pressure. In addition, ...
Added: October 11, 2019
Density Functional Theory Model for Adsorption-Induced Deformation of Mesoporous Materials with Nonconvex Pore Geometry
, , , Journal of Physical Chemistry C 2020 Vol. 124 No. 37 P. 20046-20054
Adsorption of fluids in nanoporous media causes mechanical stresses which results in deformation. This phenomenon is ubiquitous and its magnitude depends on the pore size and geometry. Adsorption and adsorption-induced deformation are typically modeled in slit-shape or convex (cylindrical or spherical) pores. However, many porous materials are composed of spherical grains, so that the pores ...
Added: August 13, 2020
Impregnation of Poly(methyl methacrylate) with Carbamazepine in Supercritical Carbon Dioxide: Molecular Dynamics Simulation
, , , Journal of Physical Chemistry B 2020 Vol. 124 No. 38 P. 8410-8417
Fully atomistic molecular dynamics simulations are employed to study impregnation of the poly(methyl methacrylate) (PMMA) matrix with carbamazepine (CBZ) in supercritical carbon dioxide. The simulation box consists of 108 macromolecules of the polymer sample with the polymerization degree of 100, 57 molecules of CBZ, and 242,522 CO2 molecules. The simulation is performed at 333 K and ...
Added: September 16, 2020
, , et al., Journal of Materials Chemistry C 2023
In spite of decades of comprehensive studies phenomenon of single semiconductor colloidal quantum dots (QD) photoluminescence (PL) blinking require theoretical retreatment. Here we present enhanced model which proposes, that the blinking is caused by fluctuations in the rate of nonradiative relaxation due to temporal variations of the electron-phonon interaction coupling. The model quantitatively reproduces the ...
Added: May 16, 2023
, , , Journal of Alloys and Compounds 2020 Vol. 836 P. 155472
The effect of tensile stresses on the magnetic properties of amorphous microwires with positive magnetostriction has been studied. It has been determined that the experimental dependence of coercivity on the tensile stresses is reversible and consists of linear and square root parts. The evolution of an average stress level in the “core” and surface domain layer has been ...
Added: December 24, 2020
, М. : ЛЕНАНД, 2020
Within the presented monograph for the first time statistical approaches, based on the self-consistent field theory, were presented for the theoretical description of the thermodynamic properties of the ion-molecular systems (electrolyte solutions, ionic liquids, dielectric polymers and metal-organic frameworks) in the bulk solution and at the interfaces with the account for their molecular structure. In ...
Added: November 18, 2019
, , et al., Journal of Physical Chemistry C 2019 Vol. 123 No. 16 P. 10333-10338
In this manuscript, we study the electrically induced breathing of Metal-Organic Framework (MOF) within a 2D lattice model. The Helmholtz free energy of the MOF in electric eld consists of two parts: the electrostatic energy of the dielectric body in the external electric eld and elastic energy of the framework. The rst contribution is calculated ...
Added: April 1, 2019
, , et al., Journal of Physical Chemistry C 2021 Vol. 125, No. 10 P. 5549-5558
Defects introduced to the surface of Bi(111) break the translational symmetry and modify the surface states locally. We present a theoretical and experimental study of the 2D defects on the surface of Bi(111) and the states that they induce. Bi crystals cleaved in ultrahigh vacuum (UHV) at low temperature (110 K) and the resulting ion-etched ...
Added: December 5, 2021
, , Applied Physics A: Materials Science and Processing 2018 Vol. 124 P. 365
Hummer’s method was used to prepare graphene oxide (GO) by chemical exfoliation of graphite. Simple precipitation method was used for the preparation of hybrid nanocomposites MgO–rGO and Fe2O3–rGO. A 0.3 Molar of corresponding metal nitrate solution and GO solution are used for the preparation process. XRD, FT-IR, and XPS were used to characterize the prepared ...
Added: January 28, 2020
, , , Carbon 2021 Vol. 175 P. 202-214
Based on the quantum-mechanical theory of electron transfer (ET), the parameter was proposed to describe the electrochemical activity of doped graphenes. The parameter is calculated using the density of states (DOS), local density of state (LDOS) values, which are in turn obtained from the density functional theory (DFT) calculations and reorganization energies of redox system. ...
Added: January 12, 2021
, Physical Chemistry Chemical Physics 2020 Vol. 22 P. 14756-14772
In this article, I summarize my theoretical developments in the statistical field theory of salt solutions of zwitterionic and multipolar molecules. Based on the Hubbard-Stratonovich integral transformation, I represent configuration integrals of dilute salt solutions of zwitterionic and multipolar molecules in the form of functional integrals over the space-dependent fluctuating electrostatic potential. In the mean-field ...
Added: June 11, 2020