
Yury A. BudkovNational Research University Higher School of Economics | HSE · Laboratory of Computational Physics
Yury A. Budkov
PhD, Doctor of Science
Applications of statistical mechanics in physical chemistry: soft matter, ionic fluids, interfaces.
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Introduction
Yury A. Budkov is a theoretical physicist whose scientific interests revolve around the applications of statistical physics to issues that emerge in physical chemistry, chemical physics, and materials science.
Publications
Publications (148)
This extended article presents a thermomechanical approach for calculating the stress tensor from the thermodynamic potential of inhomogeneous fluids and some applications to ionic fluids. The technique, based on the invariance of the fluid’s thermodynamic potential with respect to spatial transformations of translation and rotation, offers an alte...
In this paper, we use the formalism of finite-temperature quantum field theory to investigate the Casimir force between flat, ideally conductive surfaces containing confined, but mobile ions. We demonstrate that in the Gaussian approximation, the contribution of ionic fluctuations is separate from the contribution of electromagnetic fluctuations th...
This paper presents a mean field theory of electrolyte solutions, extending the classical Debye–Hückel–Onsager theory to provide a detailed description of the electrical conductivity in strong electrolyte solutions. The theory systematically incorporates the effects of ion specificity, such as steric interactions, hydration of ions, and their spati...
In this work, we present a mean‐field model that takes into account the key components of electrical double layer theory at the interface between an electrode and an electrolyte solution. The model considers short‐range specific interactions between different species, including electrode‐ion repulsion, the hydration of ions, dielectric saturation o...
This extended article presents a thermomechanical approach for calculating the stress tensor from the thermodynamic potential of inhomogeneous fluids and some applications to ionic fluids. The technique, based on the invariance of the fluid's thermodynamic potential with respect to spatial transformations of translation and rotation, offers an alte...
Room temperature ionic liquids show great promise as electrolytes in various technological applications, such as energy storage or electrotunable lubrication. These applications are particularly intriguing due to the specific behavior of ionic liquids in nanoconfinement. While previous research has been focused on optimizing the required characteri...
In this introductory chapter, we will revisit some fundamental concepts of equilibrium statistical mechanics of simple fluids, which are fluids whose molecules interact through pair-additive central potentials. We will also demonstrate the application of statistical field theory to the description of these fluids.
In this chapter, we discuss the mathematical concepts that are essential to an understanding of the subsequent material in the book. We delve into fundamental concepts such as the functional, functional derivatives, and functional integrals. Additionally, we explore Gaussian functional integrals and integrals over a Gaussian measure. We introduce t...
In this chapter, we formulate modified Poisson-Boltzmann equations that take into account not only the excluded volume, but also the ionic chemical specificity like static polarizability and dipole moment and structural effects. We then delve into practical applications of the theory across a range of diverse physical scenarios.
In this chapter, we continue the formulation of statistical field theory for ionic fluids using the grand canonical ensemble approach. This approach allows us to take into account the excluded volume of ions and to derive the modified Poisson-Boltzmann equations that describe the system more accurately. Additionally, the grand canonical framework m...
In this chapter, we formulate field-theoretic models of fluids that consider the details of the internal charge distribution of their particles, and utilize these models to evaluate the thermodynamic functions of the fluid.
In previous chapter, we discussed theoretical approaches based on self-consistent field theory for describing the thermodynamic properties of fluids composed of electrically neutral particles interacting via short-range potentials. In this chapter we formulate the statistical field theory of ionic fluids within the canonical ensemble. Much of the f...
This book presents statistical physics methods based on self-consistent field theory for describing the thermodynamic properties of ion-molecular systems, including electrolyte solutions, ionic liquids, polymeric ionic liquids, and metal-organic complexes. The methods are applicable in both the bulk and at interfaces, taking into account the molecu...
The paper presents a mean field theory of electrolyte solutions, extending the classical Debye-Hückel-Onsager theory to provide a detailed description of the electrical conductivity in strong electrolyte solutions. The theory systematically incorporates the effects of ion specificity, such as steric interactions, hydration of ions, and their spatia...
We present a quantum theory of Casimir forces between perfect electrical conductors, based on quantum electrodynamics and quantum statistical physics. This theory utilizes Kapusta's finite-temperature quantum field theory, combined with the Faddeev-Popov ghost formalism. This approach allows us to calculate Casimir forces at finite temperatures, pr...
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 component...
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 component...
In this paper, we introduce a statistical field theory that describes the macroscopic mechanical forces in inhomogeneous Coulomb fluids. Our approach employs the generalization of Noether’s first theorem for the case of a fluctuating order parameter to calculate the stress tensor for Coulomb fluids. This tensor encompasses the mean-field stress ten...
Based on the variational field theory framework, we extend our previous mean-field formalism [Y. A. Budkov and A. L. Kolesnikov, JStatMech 2022, 053205.2022], taking into account the electrostatic correlations of the ions. We employ a general covariant approach and derive a total stress tensor that considers the electrostatic correlations of ions....
Based on the variational field theory framework, we extend our previous mean-field formalism, taking into account the electrostatic correlations of the ions. We employ a general covariant approach and derive a total stress tensor that considers the electrostatic correlations of ions. This is accomplished through an additional term that depends on t...
We utilize the self-consistent field theory to explore the mechanical and electrical properties of charged surfaces immersed in polyelectrolyte solutions that could be potentially useful for electrochemical applications. Our research focuses on how the dielectric heterogeneity of the solution could affect the disjoining pressure and differential ca...
In this paper, we introduce a statistical field theory that describes the macroscopic mechanical forces in inhomogeneous Coulomb fluids. Our approach employs the
generalization of Noether’s first theorem for the case of fluctuating order parameter, to calculate the stress tensor for Coulomb fluids. This tensor encompasses the mean-field stress tens...
In this paper, we present a continuation of our research on modeling electrolyte solutions within charged pores. We make use of the model developed by Blossey et al. [Phys. Rev. E 95, 060602 (2017)], which takes into account the structural interactions between ions through a bilinear form over the gradients of local ionic concentrations in the gran...
In this paper, we present a continuation of our research on modeling electrolyte solutions within charged slit pores. We make use of the model developed by Blossey et al., which takes into account the structural interactions between ions through a bilinear form over the gradients of local ionic concentrations in the grand thermodynamic potential, a...
In this paper, we present a covariant approach that utilizes Noether’s second theorem to derive a symmetric stress tensor from the grand thermodynamic potential functional. We focus on the practical case where the density of the grand thermodynamic potential is dependent on the first and second coordinate derivatives of the scalar order parameters....
Based on the random phase approximation, we develop a molecular theory of self-coacervation in zwitterionic polymer solutions. We show that the interplay between the volume interactions of the monomeric units and electrostatic correlations of charged groups on a polymer backbone can result in liquid-liquid phase separation (self-coacervation). We a...
We utilize the self-consistent field theory to explore the mechanical and electrical properties of charged surfaces immersed in polyelectrolyte solutions that could be potentially useful for electrochemical applications. Our research focuses on how the dielectric heterogeneity of the solution could affect the disjoining pressure and differential ca...
In this paper, we present a general covariant approach based on application of the Noether's second theorem for derivation of the symmetric stress tensor from the grand thermodynamic potential functional. We consider practically important case when the density of the grand thermodynamic potential depends on the first and second coordinate derivativ...
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 polym...
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 a...
Porous carbon is well known as a good candidate for the development of electrochemical double-layer capacitors. Predominantly, many conventional carbons are microporous and often well described by the assumption of slit pore geometry. However, there is a class of carbons that is significantly different from the others, namely templated mesoporous c...
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 polym...
The number of electrochemical applications of ionic liquids and their polymerized forms is steadily growing. Nevertheless, polymeric ionic liquid-based electrochemical systems have hardly ever been described theoretically in the same way as monomeric ionic liquids-based ones. In this opinion we briefly outline recent studies addressing basic and ap...
Theoretical modeling of water adsorption in micro- and mesoporous materials remains a challenging problem for physical chemistry and chemical engineering despite its great importance for industrial applications. Here, we present the theoretical study of bulk and inhomogeneous water within the classical density functional theory. Our model includes...
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 o...
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 equation as the Euler-Lagrange equation for the obtain...
Porous carbon is well known as a good candidate for the development of electrochemical double-layer capacitors. Predominantly, many conventional carbons are microporous and often well described by the assumption of slit pore geometry. However, there is a class of carbons that is significantly different from the others, namely templated mesoporous c...
A model is developed for describing the transport of charged colloidal particles in an evaporating sessile droplet on the electrified metal substrate in the presence of a solvent flow. The model takes into account the electric charge of colloidal particles and small ions produced by electrolytic dissociation of the active groups on the colloidal pa...
Based on the random phase approximation, we develop a molecular theory of self-coacervation in zwitterionic polymer solutions. We show that the interplay between the volume interactions of the monomeric units and electrostatic correlations of charged groups on a polymer backbone can result in liquid-liquid phase separation (self-coacervation). We a...
A full-atomic classical molecular dynamics simulation of polylactide nanoparticle impregnation with carbamazepine in supercritical carbon dioxide was performed. The effect of temperature (333 K, 373 K), pressure (20 MPa, 40 MPa) and ethanol addition (1.7 mol.%) on the impregnation process was studied. Based on the solvent accessible surface area va...
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.
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 th...
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...
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 th...
We present the results of calculation of the solvation free energy, based on the classical density functional theory, for a series of 1,2,4-thiadiazole derivatives in supercritical carbon dioxide at three temperatures (308.15, 318.15 and 128.15). Using the obtained data, the solubility values of the chosen compounds are determined. The correlation...
Adsorption-induced deformation is a change in geometrical dimensions of an adsorbent material caused by gas or liquid adsorption on its surface. This phenomenon is universal and sensitive to adsorbent properties, which makes its prediction a challenging task. However, the pure academic interest is complemented by its importance in a number of engin...
A model is developed for describing transport of colloidal silica particles in an evaporating aqueous sessile droplet on the electrified metal substrate in the presence of a solvent flow. The model takes into account the electric charge of colloidal particles and small ions produced by electrolytic dissociation of the active groups on the colloidal...
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...
Modeling aggregation of ionic micelles in solution is an important task that has been attracting attention for years. The molecular-thermodynamic micellization models describe the electrostatic interactions within the Poisson-Boltzmann theory that does not take into account fluctuations of the surfactant heads in the micelle. In this work we apply...
We formulate a general mean-field theory of 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 ra...
Despite the modern level of development of computational chemistry methods and technological progress, fast and accurate determination of solvation free energy remains a huge problem for physical chemists. In this paper, we describe two computational schemes that can potentially solve this problem. We consider systems of poorly soluble drug compoun...
Despite the modern level of development of computational chemistry methods and technological progress, fast and accurate determination of solvation free energy remains a huge problem for physical chemists. In this paper, we describe two computational schemes that can potentially solve this problem. We consider systems of poorly soluble drug compoun...
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 ch...
We investigate a well-known phenomenon of the appearance of the crossover points, corresponding to the intersections of the solubility isotherms of the solid compound in supercritical fluid. Opposed to the accepted understanding of the existence of two fixed crossover points, which confine the region of the inverse isobaric temperature dependence o...
We investigate a well-known phenomenon of the appearance of the crossover points, corresponding to the intersections of the solubility isotherms of the solid compound in supercritical fluid. Opposed to the accepted understanding of the existence of two fixed crossover points, which confine the region of the inverse isobaric temperature dependence o...
Using the path integral approach, we obtain the characteristic functions of the gyration radius distributions for Gaussian star and Gaussian rosette macromolecules. We derive the analytical expressions for cumulants of the both distributions. Applying the steepest descent method, we estimate the probability distribution functions of the gyration ra...
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...
Supplementary Materials
«Electrocatalytic Activity of Doped Graphene: Quantum-mechanical Theory View»
Supplementary data contain the DOS and LDOS graphs for atoms in graphene, calculation data of the matrix element and tables with data from the main text of the article. Part of the materials contains a more detailed analysis of theoretical points.
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 reorganiza...
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...
Mesoporous materials play an important role both in engineering applications and in fundamental research of confined fluids. Adsorption goes hand in hand with the deformation of the absorbent, which has positive and negative sides. It can cause sample aging or can be used in sensing technology. Here, we report the theoretical study of adsorption-in...
MgPd2 is an intermetallic compound with a reversible hydrogen uptake near ambient conditions. Hydrogenation occurs near room temperature at pressures below 0.1 MPa to form a hydrogen-rich MgPd2H0.88 phase. In this work, hydrogen sorption isotherms were measured at 283 K ≤ T ≤ 328 K as well as at a cryogenic temperature of 77 K and pressure values u...
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...
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 comp...
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 cat...
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 cat...
In this paper we formulate a nonlocal density functional theory of inhomogeneous water. We model a water molecule as a couple of oppositely charged sites. The negatively charged sites interact with each other through the Lennard-Jones potential (steric and dispersion interactions), square-well potential (short-range specific interactions due to ele...
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...
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...
In this paper we present our study of carbamazepine solubility in supercritical carbon dioxide. We have calculated the solubility values along two isochores corresponding to the CO2 densities ρ=1.1ρcr(CO2) and ρ=1.3ρcr(CO2), where ρcr(CO2) is the critical density of CO2, in the temperature range from 313 to 383 K, as well as along three isotherms a...
Using the integral transformation, the field-theoretical Hamiltonian of the statistical field theory of fluids is obtained along with the microscopic expressions for the coefficients of the Hamiltonian. Applying this approach to the liquid-vapor interface, we derive an explicit analytical expression for the surface tension in terms of temperature,...
Using the integral transformation, the field-theoretical Hamiltonian of the statistical field theory of fluids is obtained, along with the microscopic expressions for the coefficients of the Hamiltonian. Applying this approach to the liquid-vapor interface, we derive an explicit analytical expression for the surface tension in terms of temperature,...
In this paper we formulate a nonlocal density functional theory of inhomogeneous water. We model a water molecule as a couple of oppositely charged sites. The negatively charged sites interact with each other through the Lennard-Jones potential (steric and dispersion interactions), square-well potential (short-range specific interactions due to ele...
In this paper we present our study of carbamazepine solubility in supercritical carbon dioxide. We have calculated the solubility values along two isochores corresponding to the CO$_2$ densities $\rho = 1.1\rho_{cr}(CO_2)$ and $\rho= 1.3\rho_{cr}(CO_2)$, where $\rho_{cr}(CO_2)$ is the critical density of CO$_2$, in the temperature range from $313$...
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 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, temperatu...