arXiv subjects

Zhenli Xu

Publications and source records attributed to Zhenli Xu.

70 records · Page 4Linked to original sources

arXiv2018

Harmonic surface mapping algorithm for fast electrostatic sums

We propose a harmonic surface mapping algorithm (HSMA) for electrostatic pairwise sums of an infinite number of image charges. The images are induced by point sources within a box due to a specific boundary condition which can be non-periodic. The HSMA first introduces an auxiliary surface such that the contribution of images outside the surface can be approximated by the least-squares method using spherical harmonics as basis functions. The so-called harmonic surface mapping is the procedure to transform the approximate solution into a surface charge and a surface dipole over the auxiliary surface, which becomes point images by using numerical integration. The mapping procedure is independent of the number of the sources and is considered to have a low complexity. The electrostatic interactions are then among those charges within the surface and at the integration points, which are all the form of Coulomb potential and can be accelerated straightforwardly by the fast multipole method to achieve linear scaling. Numerical calculations of the Madelung constant of a crystalline lattice, electrostatic energy of ions in a metallic cavity, and the time performance for large-scale systems show that the HSMA is accurate and fast, and thus is attractive for many applications.

physics.comp-ph↗

arXiv2017

Modified Poisson-Nernst-Planck model with accurate Coulomb correlation in variable media

We derive a set of modified Poisson-Nernst-Planck (mPNP) equations for ion transport from the variation of the free energy functional which includes the many-body Coulomb correlation in media of variable dielectric coefficient. The correlation effects are considered through the Debye charging process in which the self energy of an ion is governed by the generalized Debye-Hückel equation. We develop the asymptotic expansions of the self energy taking the ion radius as the small parameter such that the multiscale model can be solved efficiently by numerical methods. It is shown that the variations of the energy functional give the self-energy-modified PNP equations which satisfy a proper weak formulation. We present numerical results from different asymptotic expansions with a semi-implicit conservative numerical method and investigate the effect of the Coulomb correlation.

physics.comp-ph↗

arXiv2016

Understanding depletion induced like-charge attraction from self-consistent field model

The interaction force between likely charged particles/surfaces is usually repulsive due to the Coulomb interaction. However, the counterintuitive like-charge attraction in electrolytes has been frequently observed in experiments, which has been theoretically debated for a long time. It is widely known that the mean field Poisson-Boltzmann theory cannot explain or predict this anomalous feature since it ignores many-body properties. In this paper, we develop efficient algorithm and perform the force calculation between two interfaces using a set of self-consistent equations which properly takes into account the electrostatic correlation and the dielectric-boundary effects. By solving the equations and calculating the pressure with the Debye-charging process, we show that the self-consistent equations could be used to study the attraction between like-charge surfaces from weak-coupling to mediate-coupling regime, and that the attraction is due to the electrostatics-driven entropic force which is significantly enhanced by the dielectric depletion of mobile ions. A systematic investigation shows that the interaction forces can be tuned by material permittivity, ionic size and valence, and salt concentration, and that the like-charge attraction exists only for specific regime of these parameters.

cond-mat.soft↗

arXiv2015

A Multi-scale Monte Carlo Method for Electrolytes

Artifacts arise in the simulations of electrolytes using periodic boundary conditions (PBC). We show the origin of these artifacts are the periodic image charges and the constraint of charge neutrality inside the simulation box, both of which are unphysical from the view point of real systems. To cure these problems, we introduce a multi-scale Monte Carlo method, where ions inside a spherical cavity are simulated explicitly, whilst ions outside are treated implicitly using continuum theory. Using the method of Debye charging, we explicitly derive the effective interactions between ions inside the cavity, arising due to the fluctuations of ions outside. We find that these effective interactions consist of two types: 1) a constant cavity potential due to the asymmetry of the electrolyte, and 2) a reaction potential that depends on the positions of all ions inside. Combining the Grand Canonical Monte Carlo (GCMC) with a recently developed fast algorithm based of image charge method, we perform a multi-scale Monte Carlo simulation of symmetric electrolytes, and compare it with other simulation methods, including PBC+GCMC method, as well as large scale Monte Carlo simulation. We demonstrate that our multi-scale MC method is capable of capturing the correct physics of a large system using a small scale simulation.

cond-mat.soft↗

arXiv2014

Self-consistent field model for strong electrostatic correlations and inhomogeneous dielectric media

Electrostatic correlations and variable permittivity of electrolytes are essential for exploring many chemical and physical properties of interfaces in aqueous solutions. We propose a continuum electrostatic model for the treatment of these effects in the framework of the self-consistent field theory. The model incorporates a space-or field-dependent dielectric permittivity and an excluded ion-size effect for the correlation energy. This results in a self-energy modified Poisson-Nernst-Planck or Poisson-Boltzmann equation together with state equations for the self energy and the dielectric function. We show that the ionic size is of significant importance in predicting a finite self energy for an ion in an inhomogeneous medium. Asymptotic approximation is proposed for the solution of a generalized Debye-Huckel equation, which has been shown to capture the ionic correlation and dielectric self energy. Through simulating ionic distribution surrounding a macroion, the modified self-consistent field model is shown to agree with particle-based Monte Carlo simulations. Numerical results for symmetric and asymmetric electrolytes demonstrate that the model is able to predict the charge inversion at high correlation regime in the presence of multivalent interfacial ions which is beyond the mean-field theory, and also show strong effect to double layer structure due to the space- or field-dependent dielectric permittivity.

cond-mat.soft↗

arXiv2014

Self-energy-modified Poisson-Nernst-Planck equations: WKB approximation and finite-difference approaches

We propose a modified Poisson-Nernst-Planck (PNP) model to investigate charge transport in electrolytes of inhomogeneous dielectric environment. The model includes the ionic polarization due to the dielectric inhomogeneity and the ion-ion correlation. This is achieved by the self energy of test ions through solving a generalized Debye-Hückel (DH) equation. We develop numerical methods for the system composed of the PNP and DH equations. Particularly, towards the numerical challenge of solving the high-dimensional DH equation, we developed an analytical WKB approximation and a numerical approach based on the selective inversion of sparse matrices. The model and numerical methods are validated by simulating the charge diffusion in electrolytes between two electrodes, for which effects of dielectrics and correlation are investigated by comparing the results with the prediction by the classical PNP theory. We find that, at the length scale of the interface separation comparable to the Bjerrum length, the results of the modified equations are significantly different from the classical PNP predictions mostly due to the dielectric effect. It is also shown that when the ion self energy is in weak or mediate strength, the WKB approximation presents a high accuracy, compared to precise finite-difference results.

physics.comp-ph↗

arXiv2014

Electrostatic interaction in the presence of dielectric interfaces and polarization-induced like-charge attraction

Electrostatic polarization is important in many nano-/micro-scale physical systems such as colloidal suspensions, biopolymers, and nanomaterials assembly. The calculation of polarization potential requires an efficient algorithm for solving 3D Poisson's equation. We have developed a useful image charge method to rapid evaluation of the Green's function of the Poisson's equation in the presence of spherical dielectric discontinuities. This paper presents an extensive study of this method by giving an convergence analysis and developing a coarse-graining algorithm. The use of the coarse graining could reduce the number of image charges to around a dozen, by 1-2 orders of magnitude. We use the algorithm to investigate the interaction force between likely charged spheres in different dielectric environments. We find the size and charge asymmetry leads to an attraction between like charges, in agreement with existing results. Furthermore, we study three-body interaction and find in the presence of an external interface, the interaction force depends on the curvature of the interface, and behavior a non-monotonic electrostatic force.

cond-mat.soft↗

arXiv2014

Simulation of Electric Double Layers around Charged Colloids in Aqueous Solution of Variable Permittivity

The ion distribution around charged colloids in solution has been investigated intensely during the last decade. However, few theoretical approaches have included the influence of variation in the dielectric permittivity within the system, let alone in the surrounding solvent. In this article, we introduce two relatively new methods that can solve the Poisson equation for systems with varying permittivity. The harmonic interpolation method (HIM) approximately solves the Green's function in terms of a spherical harmonics series, and thus provides analytical ion-ion potentials for the Hamiltonian of charged systems. The Maxwell Equations Molecular Dynamics (MEMD) algorithm features a local approach to electrostatics, allowing for arbitrary local changes of the dielectric constant. We show that the results of both methods are in very good agreement. We also found that the renormalized charge of the colloid, and with it the effective far field interaction, significantly changes if the dielectric properties within the vicinity of the colloid are changed.

cond-mat.soft↗

arXiv2013

Efficient Implementation of the Barnes-Hut Octree Algorithm for Monte Carlo Simulations of Charged Systems

Computer simulation with Monte Carlo is an important tool to investigate the function and equilibrium properties of many systems with biological and soft matter materials solvable in solvents. The appropriate treatment of long-range electrostatic interaction is essential for these charged systems, but remains a challenging problem for large-scale simulations. We have developed an efficient Barnes-Hut treecode algorithm for electrostatic evaluation in Monte Carlo simulations of Coulomb many-body systems. The algorithm is based on a divide-and-conquer strategy and fast update of the octree data structure in each trial move through a local adjustment procedure. We test the accuracy of the tree algorithm, and use it to perform computer simulations of electric double layer near a spherical interface. It has been shown that the computational cost of the Monte Carlo method with treecode acceleration scales as $\log N$ in each move. For a typical system with ten thousand particles, by using the new algorithm, the speed has been improved by two orders of magnitude from the direct summation.

physics.comp-ph↗

arXiv2013

Solving Fluctuation-Enhanced Poisson-Boltzmann Equations

Electrostatic correlations and fluctuations in ionic systems can be described within an extended Poisson-Boltzmann theory using a Gaussian variational form. The resulting equations are challenging to solve because they require the solution of a non-linear partial differential equation for the pair correlation function. This has limited existing studies to simple approximations or to one-dimensional geometries. In this paper we show that the numerical solution of the equations is greatly simplified by the use of selective inversion of a finite difference operator which occurs in the theory. This selective inversion preserves the sparse structure of the problem and leads to substantial savings in computer effort. In one and two dimensions further simplifications are made by using a mixture of selective inversion and Fourier techniques.

physics.comp-ph↗

arXiv2013

Mellin Transform and Image Charge Method for Dielectric Sphere in an Electrolyte

We revisit the image charge method for the Green's function problem of the Poisson-Boltzmann equation for a dielectric sphere immersed in ionic solutions. Using finite Mellin transformation, we represent the reaction potential due to a source charge inside the sphere in terms of one dimensional distribution of image charges. The image charges are generically composed of a point image at the Kelvin point and a line image extending from the Kelvin point to infinity with an oscillatory line charge strength. We further develop an efficient and accurate algorithm for discretization of the line image using Padé approximation and finite fraction expansion. Finally we illustrate the power of our method by applying it in a multiscale reaction-field Monte Carlo simulation of monovalent electrolytes.

physics.comp-ph↗

arXiv2012

Effects of image charges, interfacial charge discreteness, and surface roughness on the zeta potential of spherical electric double layers

We investigate the effects of image charges, interfacial charge discreteness, and surface roughness on spherical electric double layers in electrolyte solutions with divalent counter-ions in the setting of the primitive model. By using Monte Carlo simulations and the image charge method, the zeta potential profile and the integrated charge distribution function are computed for varying surface charge strengths and salt concentrations. Systematic comparisons were carried out between three distinct models for interfacial charges: 1) SURF1 with uniform surface charges, 2) SURF2 with discrete point charges on the interface, and 3) SURF3 with discrete interfacial charges and finite excluded volume. By comparing the integrated charge distribution function (ICDF) and potential profile, we argue that the potential at the distance of one ion diameter from the macroion surface is a suitable location to define the zeta potential. In SURF2 model, we find that image charge effects strongly enhance charge inversion for monovalent interfacial charges, and strongly suppress charge inversion for multivalent interfacial charges. For SURF3, the image charge effect becomes much smaller. Finally, with image charges in action, we find that excluded volumes (in SURF3) suppress charge inversion for monovalent interfacial charges and enhance charge inversion for multivalent interfacial charges. Overall, our results demonstrate that all these aspects, i.e., image charges, interfacial charge discreteness, their excluding volumes have significant impacts on the zeta potential, and thus the structure of electric double layers.

cond-mat.soft↗

arXiv2011

From Over-charging to Like-charge Attraction in the Weak Coupling Regime

Despite decades of intensive studies, the effective interactions between strongly charged colloids still remain elusive. Here we show that a strongly charged surface with a layer of condensed counter- ions behaves effectively as a conductor, due to the mobile nature of the condensed ions. An external source charge in its vicinity is therefore attracted towards the surface, due to the image charge effect. This mechanism leads to correlational energies for counter-ions condensed on two distinct surfaces, as well as for free ions in the bulk. Generalizing Debye-Huckel theory and image charge methods, we analytically calculate these correlation energies for the two-plates problem, at the iso-electric point, where condensed counterions precisely balance the bare surface charges. At this point, the effective interaction between two plates is always attractive at small separation and repulsive at large separation.

cond-mat.soft↗

arXiv2008

A unified approach to split absorbing boundary conditions for nonlinear Schrödinger equations

An efficient method is proposed for numerical solutions of nonlinear Schrödinger equations in an unbounded domain. Through approximating the kinetic energy term by a one-way equation and uniting it with the potential energy equation, absorbing boundary conditions are designed to truncate the unbounded domain, which are in nonlinear form and can perfectly absorb the waves outgoing from the truncated domain. We examine the stability of the induced initial boundary value problems defined on the computational domain with the boundary conditions by a normal mode analysis. Numerical examples are given to illustrate the stable and tractable advantages of the method.

math.NA↗

arXiv2007

Adaptive absorbing boundary conditions for Schrodinger-type equations: application to nonlinear and multi-dimensional problems

We propose an adaptive approach in picking the wave-number parameter of absorbing boundary conditions for Schrödinger-type equations. Based on the Gabor transform which captures local frequency information in the vicinity of artificial boundaries, the parameter is determined by an energy-weighted method and yields a quasi-optimal absorbing boundary conditions. It is shown that this approach can minimize reflected waves even when the wave function is composed of waves with different group velocities. We also extend the split local absorbing boundary (SLAB) method [Z. Xu and H. Han, {\it Phys. Rev. E}, 74(2006), pp. 037704] to problems in multidimensional nonlinear cases by coupling the adaptive approach. Numerical examples of nonlinear Schrödinger equations in one- and two dimensions are presented to demonstrate the properties of the discussed absorbing boundary conditions.

math.NA↗

arXiv2005

Numerical Solitons of Generalized Korteweg-de Vries Equations

We propose a numerical method for finding solitary wave solutions of generalized Korteweg-de Vries equations by solving the nonlinear eigenvalue problem on an unbounded domain. The artificial boundary conditions are obtained to make the domain finite. We specially discuss the soliton solutions of the K(m, n) equation and KdV-K(m,n) equation. Furthermore for the mixed models of linear and nonlinear dispersion, the collision behaviors of soliton-soliton and soliton-antisoliton are observed.

math-ph↗