To what extent of ion neutralization can multivalent ion distributions around RNA-like macroions be described by Poisson-Boltzmann theory?

Nucleic acids are negatively charged biomolecules, and metal ions in solutions are important to their folding structures and thermodynamics, especially multivalent ions. However, it has been suggested that the binding of multivalent ions to nucleic acids cannot be quantitatively described by the well-established Poisson-Boltzmann(PB) theory. In this work, we made extensive calculations of ion distributions around various RNA-like macroions in divalent and trivalent salt solutions by PB theory and Monte Carlo(MC) simulations. Our calculations show that PB theory appears to underestimate multivalent ion distributions around RNA-like macroions while can reliably predict monovalent ion distributions. Our extensive comparisons between PB theory and MC simulations indicate that when an RNA-like macroion gets ion neutralization beyond a "critical" value, the multivalent ion distribution around that macroion can be approximately described by PB theory.Furthermore, an empirical formula was obtained to approximately quantify the critical ion neutralization for various RNAlike macroions in multivalent salt solutions, and this empirical formula was shown to work well for various real nucleic acids including RNAs and DNAs.     

Poisson–Boltzmann for oppositely charged bodies: an explicit derivation

The interaction between two parallel charged plates in ionic solution is a general starting point for studying colloidal complexes. An intuitive expression of the pressure exerted on the plates is usually proposed, which includes an electrostatic plus an osmotic contribution. We present here an explicit and self-consistent derivation of this formula in the only framework of the Poisson–Boltzmann (PB) theory. We also show that, depending on external constraints, the correct thermodynamic potential can differ from the usual PB free energy. For asymmetric, oppositely charged plates, the resulting expression predicts a non-trivial equilibrium position with the plates separated by a finite distance. The depth of this energy minimum is decisive for the stability of the complex. It is therefore crucial to obtain its explicit dependence on the charge densities of the plates and on the ion concentration. Analytic expressions for the position and depth of the energy minimum were derived in 1975 by Ohshima [Colloid Polym. Sci. 253, 150 (1975)] but, surprisingly, these important results seem to have been overlooked. We retrieve these expressions in a simpler formalism, more familiar to the physics community, and give a physical interpretation of the observed behavior.     

Density functional theory for polyelectrolytes near oppositely charged surfaces

We report a nonlocal density functional theory of polyelectrolyte solutions that faithfully accounts for both short- and long-range correlations neglected in a typical mean-field method. It is shown that for systems with strong electrostatic interactions, the long-range correlations are subdued by direct Coulomb attractions, thereby manifesting strong local excluded-volume effects. The theory has also been used to describe the influence of the polyion chain length and small ion valence on charge inversion due to the adsorption of polyelectrolytes at an oppositely charged surface.     

The point ion modified Poisson–Boltzmann theory for a planar electric double layer with different permittivities for the electrode,inner layer and diffuse layer

The planar electric double layer is modelled by an electrode, inner layer and diffuse layer whose constant permittivities differ. A point ion modified Poisson–Boltzmann analysis is made of the model with the ions in the diffuse layer having a distance of closest approach to the electrode, which is greater than the inner layer thickness and mimics the ion radius of a primitive model electrolyte. Comparisons are made with existing Monte Carlo simulations for uncharged and charged electrodes. For 1:1 and 2:1 electrolytes with a charged electrode, the modified Poisson–Boltzmann theory successfully predicts the singlet ion normalised density functions and the mean electrostatic potential. With the uncharged electrode, the neglect of ion size is more critical and the theoretical predictions are now poor at the higher concentrations.     

Revisiting the Poisson-Boltzmann theory: Charge surfaces, multivalent ions and inter-plate forces

The Poisson-Boltzmann (PB) theory is extensively used to gain insight on charged colloids and biological systems as well as to elucidate fundamental properties of intermolecular forces. Many works have been devoted in the past to study PB-related features and to confirm them experimentally. In this work we explore the properties of inter-plate forces in terms of different boundary conditions. We treat the cases of constant surface charge, constant surface potential and mixed boundaries. The interplay between electrostatic interactions, attractive counter-ion release, and repulsive van ’t Hoff contribution is discussed separately for each case. Finally, we discuss how the crossover between attractive and repulsive interactions for constant surface charge case is influenced by the presence of multivalent counter-ions, where it is shown that the range of the attractive interaction grows with the valency.     

Nonlinear propagation of ultra-low-frequency electromagnetic modes in a magnetized dusty plasma

A theoretical investigation has been made of nonlinear propagation of ultra-low-frequency electromagnetic waves in a magnetized two fluid (negatively charged dust and positively charged ion fluids) dusty plasma. These are modified Alfvén waves for small value of and are modified magnetosonic waves for large , where is the angle between the directions of the external magnetic field and the wave propagation. A nonlinear evolution equation for the wave magnetic field, which is known as Korteweg de Vries (K-dV) equation and which admits a stationary solitary wave solution, is derived by the reductive perturbation method. The effects of external magnetic field and dust characteristics on the amplitude and the width of these solitary structures are examined. The implications of these results to some space and astrophysical plasma systems, especially to planetary ring-systems, are briefly mentioned. Received 8 July 1999 and Received in final form 11 October 1999     

Electrostatistics of counter-ions at and between planar charged walls: From Poisson-Boltzmann to the strong-coupling theory

The Poisson-Boltzmann (PB) approach gives asymptotically exact counter-ion density profiles around macroscopic charged objects and forces between macroscopic charged objects in the weak-coupling limit of low counter-ion valency, low surface-charge density, and high temperature. In this paper we derive, using field-theoretic methods, a theory which becomes exact in the opposite limit of strong coupling (SC). Formally, it corresponds to a standard virial expansion. Long-range divergences render the virial expansion intractable for homogeneous bulk systems, giving rise to non-analyticities in the low-density expansion of the free-energy density of electrolyte solutions. We demonstrate that for the case of inhomogeneous density distribution functions at macroscopic charged bodies these divergences are renormalizable by a systematic expansion in powers of the fugacity. For a single planar charged wall, we obtain the counter-ion density profile in the SC limit, which decays exponentially, in contrast to the PB result, which predicts algebraic decay, and in agreement with previously published numerical results. Similarly and highly charged plates in the presence of multivalent counter-ions attract each other in the SC limit and form electrostatically bound states, in contrast to the PB limit, where the interaction is always repulsive. By considering next-leading corrections to both the PB and SC theories, we estimate the range of validity for both theories.     

Density functional theory study on ion adsorption and electroosmotic flow in a membrane with charged cylindrical pores†

ABSTRACT

Ion adsorption and electroosmotic flow induced by an external electric field have a variety of practical applications, especially for membrane technology. In this work, a partially perturbative density functional theory (DFT) based on the modified fundamental measure theory was applied to investigate the ion density distributions and partitions in a charged cylindrical pore. Different types of electrolyte solutions, including both charge symmetric and asymmetric, were examined using the proposed theory with various pore diameters, bulk densities, ion valencies and surface charge densities. The ion concentration profiles calculated with the theory exhibit good agreements with the results of the Monte Carlo simulations, while the results of the Poisson–Boltzmann equation deviate greatly especially for the high valence electrolytes in narrow cylindrical pores. Some interesting phenomena discovered in both experiments and simulations, such as the reverse distribution of the ions and charge inversion, can be well reproduced with the DFT. Based on the ion concentration distributions obtained from the DFT, the transient velocity profiles of the electroosmotic flow in the charged cylindrical nanopores were calculated with the Navier–Stokes (NS) equation. The characteristics of the electroosmotic flow were discussed under the different bulk electrolyte concentrations and thickness of the electric double layer inside the nanopore. The enhancement of the velocity near the pore wall, which cannot be described by the traditional theory, was well characterised by the DFT combined with the NS equation.     

Lattice and charge inhomogeneities in transition metal oxides

Transition metal oxides show an extremely rich variety of ground states which frequently can be modified through doping, pressure, temperature. The conventional understanding of these compounds as e.g. typical ionic systems or typical metallic systems yields incorrect results concerning their dynamical or electronic structures. It is shown here that the intrinsic instability of the doubly negatively charged oxygen ion O²⁻ triggers many of the unusual properties.     

Polyelectrolytes in the presence of multivalent ions: gelation versus segregation

We analyze solutions of strongly charged chains bridged by linkers such as multivalent ions. The gelation induced by the strong short range electrostatic attractions is dramatically suppressed by the long range electrostatic correlations due to the charge along the non-cross-linked monomers and ions. A modified Debye-Hückel approach of cross-linked clusters of charged chains is used to determine the mean field gelation transition self-consistently. Highly dilute polyelectrolyte solutions tend to segregate macroscopically. Semidilute solutions can form gels if the Bjerrum length l(B) and the distance between neighboring charged monomers along the chain b are both greater than the ion size a.     

Geometries,stabilities, and electronic properties analysis in In_nNi~((0,±1)) clusters: Molecular modeling and DFT calculations

Density functional theory(DFT) with the B3 LYP method and the SDD basis set is selected to investigate In_nNi,In_nNi~-, and In_nNi~+ (n = 1–14) clusters. For neutral and charged systems, several isomers and different multiplicities are studied with the aim to confirm the most stable structures. The structural evolution of neutral, cationic, and anionic In_nNi clusters, which favors the three-dimensional structures for n = 3–14. The main configurations of the In_nNi isomers are not affected by adding or removing an electron, the order of their stabilities is also nearly not affected. The obtained binding energy exhibits that the Ni-doped In_(13) cluster is the most stable species of all different sized clusters. The calculated fragmentation energy and the second-order energy difference as a function of the cluster size exhibit a pronounced even–odd alternation phenomenon. The electronic properties including energy gap(E_g), adiabatic electron affinity(AEA), vertical electron detachment energy(VDE), adiabatic ionization potential energy(AIP), and vertical ionization potential energy(VIP) are studied. The total magnetic moments show that the different magnetic moments depend on the number of the In atoms for charged In_nNi. Additionally, the natural population analysis of In_nNi~((0,±1)clusters is also discussed.     

On the Nonlinear Excitation in Self Gravitating Quantum Dusty Plasma

Nonlinear excitation in self gravitating quantum dusty plasma is analysed from the viewpoint of perturbation theory. A plasma configuration consisting of electron, ion and dust particles are treated by reductive perturbation theory, to deduce two coupled modified KdV equations. The soliton like solutions of such coupled systems are obtained with the help of another multiple scale perturbation theory. This leads to the variation of soliton amplitude and velocity due to the several interaction terms.     

Estimation of zeta potentials of titania nanoparticles by molecular simulation

Non-equilibrium molecular dynamics (NEMD) simulations have been performed for static electric fields for a range of positively charged spherical rutile-titania nanoparticles with radii of 1.5 to 2.9 nm for two different salt concentrations in water, in order to simulate electrophoresis directly. Using the observed limiting drag velocities, Helmholtz-Smoluchowski (HS) theory was used to estimate their ζ potentials. These estimates were compared to values from numerical solution of the non-linear Poisson-Boltzmann (PB) equation for representative configurations of the nanoparticles, in addition to idealised analytic and Debye-Hückel (DH) solutions about spherical particles of the same geometry and charge state, for the given salt concentrations. It was found that reasonable agreement was obtained between the various approaches, with the NEMD-HS results some 15%-15% smaller than the numerical PB results for more highly charged nanoparticles.     

Numerical solution of a modified Poisson-Boltzmann equation for 1 : 2 and 2 : 1 electrolytes in the diffuse layer

A modified Poisson-Boltzmann (MPB) equation for an unsymmetrically charged electrolyte in the diffuse part of the electric double layer at a plane charged wall is solved numerically using a quasi-linearization procedure. Computations are carried out for 1 : 2 and 2 : 1 restricted primitive model electrolytes with no imaging and for a metallic wall and the results compared with the classical Gouy-Chapman-Stern theory. Except for negligible surface charge, the system with a divalent counter ion is the most sensitive to any change in its physical parameters. In general the MPB mean electrostatic potential, in contrast to the Gouy-Chapman-Stern potential, is not a monotonic decreasing function. The asymptotic behaviour of the MPB equation implies charge oscillations above a critical electrolyte concentration (?0·23 M) while below this concentration imaging or surface charge-ion interactions can produce a charge inversion. Charge separation is found for no surface charge with a metallic wall. The point ion limit is briefly considered.     

Order in very cold confined plasmas

The study of the structure and dynamic properties of classical systems of charged particles confined by external forces, and cooled to very low internal energies, is the subject of this article. An infinite system of identical charged particles has been known for some time to form a body-centered cubic lattice and is a simple classical prototype for condensed matter. Recent technical developments in storage rings, ion traps, and laser cooling of ions, have made it possible to produce such systems in the laboratory, though somewhat modified because of their finite size. In this article I discuss what one may expect in such systems [1] and also show some examples of experiments.     

Quantum dynamics of Gaudin magnets

Quantum dynamics of many-body systems is a fascinating and significant subject for both theory and experiment. The question of how an isolated many-body system evolves to its steady state after a sudden perturbation or quench still remains challenging. In this paper, using the Bethe ansatz wave function, we study the quantum dynamics of an inhomogeneous Gaudin magnet. We derive explicit analytical expressions for various local dynamic quantities with an arbitrary number of flipped bath spins, such as: the spin distribution function, the spin–spin correlation function, and the Loschmidt echo. We also numerically study the relaxation behavior of these dynamic properties, gaining considerable insight into coherence and entanglement between the central spin and the bath. In particular, we find that the spin–spin correlations relax to their steady value via a nearly logarithmic scaling, whereas the Loschmidt echo shows an exponential relaxation to its steady value. Our results advance the understanding of relaxation dynamics and quantum correlations of long-range interacting models of the Gaudin type.     

A multichannel shot noise approach to describe synaptic background activity in neurons

Systems driven by Poisson-distributed quantal inputs can be described as “shot noise” stochastic processes. This formalism can apply to neurons which receive a large number of Poisson-distributed synaptic inputs of similar quantal size. However, the presence of temporal correlations between these inputs destroys their quantal nature, and such systems can no longer be described by classical shot noise processes. Here, we show that explicit expressions for various statistical properties, such as the amplitude distribution and the power spectral density, can be deduced and investigated as functions of the correlation between input channels. The monotonic behavior of these expressions allows an one-to-one relation between temporal correlations and the statistics of fluctuations. Multi-channel shot noise processes, therefore, open a way to deduce correlations in input patterns by analyzing fluctuations in experimental systems. We discuss applications such as detecting correlations in networks of neurons from intracellular recordings of single neurons.     

Proposal to Test a Transient Deviation from Quantum Mechanics’ Predictions for Bell’s Experiment

Quantum mechanics predicts correlations between measurements performed in distant regions of a spatially spread entangled state to be higher than allowed by intuitive concepts of Locality and Realism. These high correlations forbid the use of nonlinear operators of evolution (which would be desirable for several reasons), for they may allow faster-than-light signaling. As a way out of this situation, it has been hypothesized that the high quantum correlations develop only after a time longer than L/c has elapsed (where L is the spread of the entangled state and c is the velocity of light). In shorter times, correlations compatible with Locality and Realism would be observed instead. A simple hidden variables model following this hypothesis is described. It is based on a modified Wheeler–Feynman theory of radiation. This hypothesis has not been disproved by any of the experiments performed to date. A test achievable with accessible means is proposed and described. It involves a pulsed source of entangled states and stroboscopic record of particle detection during the pulses. Data recorded in similar but incomplete optical experiments are analyzed, and found consistent with the proposed model. However, it is not claimed, in any sense, that the hypothesis has been validated. On the contrary, it is stressed that a complete, specific test is absolutely needed.     

Role of polarization Bremsstrahlung in the formation of thick target Bremsstrahlung spectra in the energy range of 5–10 keV

Role of polarization Bremsstrahlung in the formation of total Bremsstrahlung (BS) spectra in thick targets of Al, Ti, Sn and Pb, produced by complete absorption of ⁹⁰Sr beta particles having an energy range of 0–546 keV, are studied in the photon energy region of 5 to 10 keV. The theoretical BS spectral photon distributions, obtained from Elwert corrected (nonrelativistic) Bethe–Heitler theory, a modified Elwert factor (relativistic) Bethe–Heitler theory that describe ordinary Bremsstrahlung (OB) and a modified Elwert factor (relativistic) Bethe–Heitler theory for BS spectra that includes the polarization Bremsstrahlung (PB) into OB in stripped atom approximation, were compared with the experimentally measured BS spectral photon distributions. It has been observed that the experimental results are in agreement with the modified Elwert factor (relativistic) Bethe–Heitler theory at photon energy from 5 to 10 keV. It has been also observed that the contribution of PB into OB decreases with increase in end‐point energy of beta emitter and the energy of the emitted photon. Further, it has been found that the contribution of PB into OB increases with increase in atomic number of the target atom. This indicates the importance of PB in the formation of BS produced by continuous beta particle. Copyright © 2012 John Wiley & Sons, Ltd.