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Yury A. Budkov

Publications and source records attributed to Yury A. Budkov.

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Localization of a quantum particle in a classical one-component plasma: fluctuation-induced random potential, localization length and mutual decoherence

We develop a microscopic theory of disorder-induced attenuation and mutual coherence degradation for a quantum particle in a classical one-component plasma. The random potential originates from equilibrium thermal fluctuations of the ionic charge density within the random phase approximation. Its correlator retains an unscreened $1/r$ tail, leading to a Coulomb logarithm in the eikonal localization scale $\ell(k)$. In the weak-disorder regime $\ell(k) \propto k^2 / \ln(κL)$, while in the strong-disorder limit $\ell \propto (\ln(κL))^{-1/3}$. Building on the same disorder model, we evaluate the mutual coherence function (Cooperon) of an electron beam and derive a closed analytical expression for the phase structure function $D_ϕ(ρ)$. At large transverse separations the coherence decays as a power law $γ(ρ)\sim ρ^{-η}$, with an exponent determined by the disorder strength. The transverse coherence length $ρ_c$ satisfies a scaling relation $ρ_c \sim λ_D \sqrt{\ell/L}$, linking the eikonal attenuation scale with the loss of quantum coherence. Numerical estimates for aqueous electrolytes under transmission electron microscopy conditions are given. A relativistic extension confirms that the same scaling holds for relativistic beams, with the eikonal coupling given by $A_{ m rel}=1/(\hbar v)$ and approaching the finite high-energy limit $1/(\hbar c)$.

physics.plasm-ph

Dynamic Coulomb disorder and eikonal attenuation of a quantum particle in a classical one-component plasma

We extend the static theory of disorder-induced exponential decay of the averaged Green function of a quantum charged particle in a classical one-component plasma to the dynamic regime. The central object of the theory is not the Anderson localization length in the strict Lyapunov sense, but the eikonal attenuation scale of the disorder-averaged propagator. The temporal evolution of the ionic density fluctuations is incorporated within the random phase approximation, and the dynamic potential correlator is derived from the fluctuation--dissipation theorem and the Kramers--Kronig relations. Within the eikonal approximation, the effective disorder strength is expressed through the longitudinal dielectric function of the ion plasma. For particles moving faster than the ion thermal speed, the static Coulomb logarithm is recovered, with the large-distance cutoff replaced by the dynamic scale $v/ω_{pi}$. For slow particles, the Coulomb logarithm disappears completely and the disorder strength becomes proportional to the velocity. Consequently, the controlled weak-disorder attenuation scale becomes proportional to $k$, instead of the usual quasi-static $k^2$ law. We also show that the full saddle-point problem in a dynamic medium contains an additional dependence on the saddle variable through the effective velocity $v_s=v/s$. In the slow-particle strong-saddle sector this self-consistency leads to a saturation scale $\ell\sim g^{-1/2}$, where $g$ is the coefficient in $G_{\rm dyn}(v)=gk$. Building on the same dynamic formalism, we evaluate the mutual coherence function in the slow weak-disorder branch and show that the transverse coherence length obeys the same parametric relation $ρ_c\simλ_D\sqrt{\ell/L}$ as in the static case.

cond-mat.stat-mech

Localization of a quantum particle in a classical one-component plasma.III. Mutual coherence and coherence degradation in Coulomb-disordered media

We derive the mutual coherence function of an electron beam propagating through a static or dynamic Coulomb-disordered medium and show that its decay introduces an intrinsic coherence-reduction mechanism relevant for electron microscopy in Coulomb-disordered media. Using the Efimov path-integral formalism, the coherence length $ρ_c$ is expressed through the same disorder correlator that governs the single-particle localization length $\ell$. For both a static electrolyte and a dynamic plasma we obtain a universal relation $ρ_c \sim λ_D \sqrt{\ell/L}$, where $λ_D$ is the Debye length and $L$ the sample thickness. In the static case $\ell\propto k^{2}$ (electron momentum), whereas in the dynamic slow-particle regime $\ell\propto k$, leading to qualitatively different energy dependences of the coherence scale. The ion thermal velocity cancels out in the final expression, demonstrating a formal connection between transverse coherence decay and longitudinal localization phenomena. Exact analytical results are given for the phase structure function of a model electrolyte, and numerical estimates indicate that disorder-induced phase decorrelation may contribute appreciably to the attenuation of high-spatial-frequency contrast under experimentally relevant liquid-cell electron microscopy conditions. Possible implications for cryo-EM, disordered liquids, soft condensed matter, and biological media are discussed. In an appendix we extend the theory to the relativistic regime relevant for transmission electron microscopy.

cond-mat.stat-mech

Relativistic saturation of Coulomb-induced electron decoherence: from eikonal phase noise to Bethe--Salpeter kinetic theory

We develop a microscopic theory of the mutual coherence and small-angle scattering of relativistic electron matter waves propagating through a Coulomb-fluctuating medium. Starting from the Dirac equation, we derive a relativistic paraxial wave equation and then obtain, rather than assume, the Bethe--Salpeter and Wigner--Boltzmann kinetic equations for the disorder-averaged two-point coherence. The Coulomb environment enters through the eikonal phase-coupling factor $A_{\rm rel}=1/(\hbar v)$, which saturates at $1/(\hbar c)$ for ultra-relativistic particles. This saturation is the central physical result: increasing the beam voltage suppresses Coulomb phase noise only up to a finite relativistic floor. We first formulate the eikonal approximation, in which the transmitted electron wave accumulates a random longitudinal phase. For a one-component Coulomb medium the electrostatic potential correlator retains a Coulomb tail, producing a logarithmic phase structure function and an algebraic decay of the transverse mutual coherence. We then go beyond the eikonal construction by deriving the Bethe--Salpeter equation for the Cooperon-like two-point coherence propagator directly from the paraxial wave equation. After a longitudinal Markov projection this equation reduces, after a Wigner transform, to a kinetic equation with a Coulomb small-angle scattering kernel. The coordinate-space solution of the same Bethe--Salpeter equation recovers the eikonal mutual coherence function, while the Wigner form additionally describes angular diffusion and transverse broadening caused by multiple small-angle scattering. The resulting theory separates three effects which are often conflated in charged-particle wave propagation: attenuation of the coherent amplitude, decay of mutual coherence, and conservative redistribution of intensity in transverse phase space.

cond-mat.dis-nn

Possible Topological Decoherence Transition in Relativistic Electron Beams Propagating through Coulomb-Disordered Media

We show that the mutual coherence of a relativistic electron beam in a Coulomb-disordered medium is governed by an effective two-dimensional compact phase field with a logarithmic correlation function. The corresponding Gaussian free-field action exhibits a stiffness inversely proportional to the propagation length. When the compact nature of the phase is taken into account, the system supports vortex excitations that interact as a two-dimensional Coulomb gas. Renormalization-group analysis of this gas indicates the existence of a critical sample thickness $L_c$ at which a Berezinskii--Kosterlitz--Thouless (BKT) transition may occur, separating a regime of algebraic decoherence from one where free vortices proliferate and coherence is destroyed exponentially. The critical thickness is expressed through fundamental microscopic parameters and could be observed in transmission electron microscopy of liquid cells or cryogenic samples.

cond-mat.dis-nn

Osmolyte-Modulated Differential Capacitance and Disjoining Pressure for Nanoconfined Electrolytes: A Modified Poisson-Boltzmann Theory

This study employs modified Poisson-Boltzmann theory to systematically investigate the influence of zwitterionic osmolyte additives to an electrolyte solution on disjoining pressure and electric differential capacitance within charged slit-like nanopores with conductive walls. We demonstrate that increasing concentrations of zwitterionic osmolytes synergistically enhance both disjoining pressure and differential capacitance, highlighting their dual role in the potential improvement of supercapacitor performance. The insights gained underscore the unique capabilities of zwitterionic osmolytes as multifunctional additives for fine-tuning the properties of electric double layers, thereby bridging the gap between capacitive efficiency and microporous electrode longevity.

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

Variational field theory of macroscopic forces in Coulomb fluids

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 the autocorrelation function of local electric field fluctuations. Utilizing the derived total stress tensor and applying the mechanical equilibrium condition, we establish a general expression for the disjoining pressure of the Coulomb fluids, confined in a pore with a slit-like geometry. Using this equation, we derive an asymptotic expression for the disjoining pressure in a slit-like pore with non-electrified conductive walls. Present theory is the basis for future modeling of the mechanical stresses that occur in electrode pores with conductive charged walls, immersed in liquid phase electrolytes beyond the mean-field theory.

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

Theory of electrolyte solutions in a slit charged pore: effects of structural interactions and specific adsorption of ions

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, as well as their steric interactions through the lattice gas model. The structural interactions may describe effects of the molecular structure of ions at a phenomenological level. For example, these effects include steric effects due to non-spherical shapes of ions, their conformation lability, and solvent effects. In addition, we explore their specific interactions with the pore walls by incorporating external attractive potentials. Our primary focus is on observing the behavior of ionic concentration profiles and the disjoining pressure as the pore width changes. By starting with the local mechanical equilibrium condition, we derive a general expression for the disjoining pressure. Our findings indicate that considering the structural interactions of ions leads to a pronounced minimum on the disjoining pressure profiles at small pore widths. We attribute this minimum to the formation of electric double layers on the electrified surfaces of the pore. Additionally, our results demonstrate that inclusion of the attractive interactions of ions with the pore walls enhances this minimum and shifts it to smaller pore thicknesses. Our theoretical discoveries may be useful for those involved in supercapacitor electrochemical engineering, particularly when working with porous electrodes that have been infused with concentrated electrolyte solutions.

cond-mat.soft

Influence of fluid flows on electric double layers in evaporating colloidal sessile droplets

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 particles and solvent molecules. We employ a system of self-consistent Poisson and Nernst--Planck equations for electric potential and average concentrations of colloidal particles and ions with the appropriate boundary conditions. The fluid dynamics, temperature distribution and evaporation process are described with the Navier--Stokes equations, equations of heat conduction and vapor diffusion in air, respectively. The developed model is used to carry out a first-principles numerical simulation of charged silica colloidal particle transport in an evaporating aqueous droplet. We find that electric double layers can be destroyed by a sufficiently strong fluid flow.

cond-mat.soft

Electric double layer theory for room temperature ionic liquids on charged electrodes: milestones and prospects

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 influence on it. Among them are parameters of short-range specific interactions, ionic diameters, static polarizabilities, and permanent dipole moments. We also discuss the recent "nonlocal" mean-field theories that can describe the overscreening behavior of the local ionic concentrations, as well as the crossover from overscreening to crowding.

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

Molecular fields and statistical field theory of fluids. Application to interface phenomena

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, density and parameters of inter-molecular potential. We also demonstrate that a clear physical interpretation may be given to the formal statistical field arising in the integral transformation - it may be associated with the one-body local microscopic potential. The results of the theory, lacking any ad-hoc or fitting parameters are in a good agreement with available simulation data.

cond-mat.stat-mech

Metal-Organic Framework Breathing in Electric Field: A Theoretical Study

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 field consists of two parts: the electrostatic energy of the dielectric body in the external electric field and elastic energy of the framework. The first contribution is calculated from the first principles of statistical mechanics with an account of MOF symmetry. By minimizing the obtained free energy and solving the resulting system of equations, we obtain the local electric field and the parameter of the unit cell (angle $α$). The paper also studies the cross-section area of the unit cell and the polarization as functions of the external electric field. We obtain the hysteresis in the region of the structural transition of the framework. Our results are in qualitative agreement with the literature data of the molecular dynamics (MD) simulation of MIL-53(Cr).

cond-mat.soft

Field-regulated force by grafted polyelectrolytes

Generation of mechanical force regulated by external electric field is studied both theoretically and by molecular dynamics (MD) simulations. The force arises in deformable bodies linked to the free end of a grafted polyelectrolyte chain which is exposed to electric field that favours its adsorption. We consider a few target bodies with different force-deformation relations including (i) linear and (ii) cubic dependences as well as (iii) Hertzian-like force. Such force-deformation relations mimic the behaviour of (i) coiled and (ii) stretched polymer chains, respectively, or (iii) that of a squeezed colloidal particle. The magnitude of the arising force varies over a wide interval although the electric field alters within a relatively narrow range only. The predictions of our theory agree quantitatively well with the results of numerical simulations. Both cases of zero and finite electrical current are investigated and we do not obtain substantial differences in the force generated. The phenomenon studied could possibly be utilised to design, e.g., vice-like devices to fix nano-sized objects.

cond-mat.stat-mech