Macroions in salty water with multivalent ions: giant inversion of charge

Screening of a strongly charged macroion by oppositely charged colloidal particles, micelles, or short polyelectrolytes is considered. Because of strong lateral repulsion such multivalent counterions form a strongly correlated liquid at the surface of the macroion. This liquid provides correlation-induced attraction of multivalent counterions to the macroion surface. As a result even a moderate concentration of multivalent counterions in the solution inverts the sign of the net macroion charge. We show that at high concentration of monovalent salt the absolute value of inverted charge can be larger than the bare one. This giant inversion of charge can be observed in electrophoresis.     

Collapse of spherical polyelectrolyte brushes in the presence of multivalent counterions

We consider the interaction of multivalent counterions with spherical polyelectrolyte brushes (SPB). The SPB result if linear polyelectrolyte (PE) chains (contour length: 60 nm) are densely grafted to colloidal spheres of 116 nm in diameter. Dispersed in water, the surface layer consisting of chains of the strong PE poly(styrene sulfonic acid) (PSS) will swell. We demonstrate that successive addition of trivalent ions (La3+) leads to a collapse in which the surface layer is shrinking drastically. All findings are discussed on the base of a theoretical mean-field approach using the Donnan equilibrium. The ion exchange and a strong binding of trivalent ions by PE chains is followed up by a drop in the osmotic pressure inside the brush. This reduction is the driving force for the collapse. The strong ion-chain correlation is discussed with results obtained from molecular dynamics simulations.     

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.     

Solubility of highly charged anionic polyelectrolytes in presence of multivalent cations: Specific interaction effect

Studies performed on strong polyelectrolytes and on a weak polyelectrolyte, sodium poly(acrylate), show that their stability in presence of multivalent cations depends on the chemical nature of the charged side groups of the polymer. For sulfonate groups (SO₃ ^-) or sulfate groups (OSO₃ ^-) phase separation generally occurs in presence of inorganic cations of valency 3 (as La³⁺) or larger and a resolubilization takes place at high salt concentration. The interactions of the polyelectrolyte with multivalent cations are of electrostatic origin and the phase diagrams are weakly dependent on the chemical nature of the polymer backbone and on the specificity of the counterions. For acrylate groups, (COO^-), the phase separation was observed with inorganic cations of valency 2 (as Ca²⁺) or larger without resolubilization at high salt concentration. The phase separation is due to a chemical association between cations and acrylate groups of two neighboring monomers of the same chain. This chemical association creates a hydrophobic complex by dehydrating both monomer and cation. With organic trivalent cation, as spermidine ⁺H₃N(CH₂)₄NH₂ ⁺(CH₂)₃NH₃ ⁺, where no chemical association occurs with the charged side groups COO^- or SO₃ ^- of the polyelectrolyte, similar phase diagrams were observed whatever was the polyelectrolyte with a resolubilization at high trivalent cation concentration. Received 3 March 1999 and Received in final form 2 September 1999     

Secondary-beam production: Protons versus heavy ions

The construction of two new-generation complementary RIB facilities in Europe, one based on the in-flight fragmentation or fission (IFF) method (FAIR) and the other on the isotope separation on-line (ISOL) method (EURISOL) is expected in the next 10-15 years. The reaction mechanisms, responsible for the production of the secondary nuclei, along with the technical constrains, have to be considered for the designs of the facilities. In this work, we study which reaction mechanisms can be exploited at best for the production of the secondary beams in the two facilities.     

Strong segregation of doped ions in Y2SiO5:Pr3+ nanocrystals

Strong temperature controlled segregation of doped ions in Y₂SiO₅:Pr³⁺ nanocrystals detected by spectroscopic techniques is reported. The elastic interactions stimulate Pr³⁺ segregation thus leading to non-uniform distribution of doped ions, pair formation and, as a consequence, to abnormal low threshold of luminescence concentration quenching for Y₂SiO₅:Pr³⁺ nanocrystals.     

Direct observation of charge inversion by multivalent ions as a universal electrostatic phenomenon

We have directly observed reversal of the polarity of charged surfaces in water upon the addition of trivalent and quadrivalent ions using atomic force microscopy. The bulk concentration of multivalent ions at which charge inversion reversibly occurs depends only very weakly on the chemical composition, surface structure, size, and lipophilicity of the ions, but is very sensitive to their valence. These results support the theoretical proposal that spatial correlations between ions are the driving mechanism behind charge inversion.     

Nonlinear instability of the ioncyclotron whistlers in presence of negative ions

This paper provides a theoretical investigation of the nonlinear propagation of ion cyclotron whistlers in presence of negative ions. First, it derives the dispersion relations from which group travel time of the ioncyclotron whistlers has been calculated. The ioncyclotron damping of the whistler due to the presence of negative ions and nonlinearity in the ionospheric plasma has also been studied here. The threshold power of the unstable proton whistler, the total attenuation and the generated magnetic field have been calculated. Finally possible applications of this study have been pointed out and the variation of different ionospheric parameters in different situations have been shown both numerically and graphically.The author is grateful to Prof. B. Chakraborty, Dept. of Mathematics, Jadavpur University; to Dr. K. P. Das, Dept. of Mathematics, Calcutta University; to Dr. S. N. Paul, Serampore Girls' College, Hooghly, West Bengal and to Dr. G. C. Das, Dept. of Mathematics, Manipur University for their helpful suggestions in the preparation of the article. The author is also grateful to the referee for his useful comments and suggestions which helped in bringing the paper in its present version.     

Three-particle recombination of non-hydrogen-like ions in the presence of plasma microfields

The effect of electric and magnetic plasma microfields on three-particle electron-ion recombination via the highly excited states of a hydrogen-like ion is studied. It is shown that electric microfields impede this process, and at some electron temperature it ceases for sufficiently high plasma density. Magnetic microfields speed up recombination via low-lying states only negligibly. The rate of such recombination into non-hydrogen-like ion states is comparatively higher than for the equivalent hydrogen-like ion states. Zh. éksp. Teor. Fiz. 114, 1230–1241 (October 1998)     

Three-body recombination of electrons and ions in the presence of two-level atoms

The distribution function of bound electrons and the recombination rate of electrons and ions in the presence of two-level atoms is considered within a diffusion model. Two cases are considered: (a) it is assumed in accordance with traditional theories that relaxation occurs as a result of binary collisions; (b) it is assumed that the anomalous drift previously discovered on the basis of a first-principles simulation takes place. It is shown that the distribution of bound electrons obtained on the basis of the theory of binary Coulomb collisions is not consistent with the results of a numerical many-particle dynamics simulation, while a kinetic model which utilizes the theory of anomalous drift is consistent with the simulation results. Zh. Tekh. Fiz. 68, 15–19 (January 1998)     

Absorption bands of lead in alkali chlorides in the presence of hydroxyl ions

Absorption studies of divalent lead in crystals and solutions of alkali chlorides with an admixture of hydroxyl ions showed that the absorption band lying at 250 nm can be attributed to hydroxochlorocomplexes of lead.It is the author's agreeable duty to thank Dr. A. Bohun for having drawn his attention to this problem and V. Piskáková for help in the absorption measurements.     

Magnetostriction of dilute rare-earth bismuthides: The effect of non-S-state ions versus “S-state” ions

Shape magnetostriction measurements along the [001] direction were carried out for dilute rare-earth bismuthides; LaBi: R (R = Ce, Sm, Gd, Tb, Er) and the antimonide LaSb: Gd. The magnetostriction of LaBi: Ce and LaBi: Sm reveal the “reverse magnetostriction” phenomenon, enabling us to extract an overall crystalline field splitting of 12 K for the former compound. The magnetostriction of LaBi: Gd and LaSb: Gd which are significantly larger than that of the “pure” hosts, can be explained by a modified version of a model previously suggested by us. The fitting procedure yields magnetoelastic coupling constants for LaSb: Gd and LaBi: Gd which has the correct sign and magnitude according to existing theories.     

Transport of charge-density waves in the presence of disorder: classical pinning versus quantum localization

We consider the interplay of the elastic pinning and the Anderson localization in the transport properties of a charge-density wave in one dimension, within the framework of the Luttinger model in the limit of strong repulsion. We address a conceptually important issue of which of the two disorder-induced phenomena limits the mobility more effectively. We argue that the interplay of the classical and quantum effects in transport of a very rigid charge-density wave is quite nontrivial: the quantum localization sets in at a temperature much smaller than the pinning temperature, whereas the quantum localization length is much smaller than the pinning length.     

Codeposition of SiC particles with electrolytic cobalt in the presence of Cs ions

Electrodeposition of SiC particles with cobalt matrix in the presence of cesium ions was studied. The influence of Cs⁺ concentration (0-37.6 mM) on the cathodic polarization curves was determined in galvanostatic and potentiodynamic measurements. It was found that the presence of Cs⁺ in the solution enhanced adsorption of Co²⁺ ions on SiC, but preferential cesium adsorption occurred simultaneously. The last phenomena resulted in cesium incorporation in the composite coating. Surface charge of SiC powder and amounts of functional groups on SiC surface were determined. The particles incorporation into deposits was only little dependent on cesium concentration in the bath. Structure of the composite coatings was studied by microscopic observations. Microhardness of the deposits was also determined.     

Tb ions in presence of ZnS:Mn nanocrystals immobilized on silica: Energy transfer ZnS→Tb and coordination state of Mn ions

Three-component luminescent material consisting of silica xerogel as a support with immobilized ZnS:Mn²⁺ nanocrystals and Tb³⁺ ions was compared with such two-component materials as the silica support with ZnS:Mn²⁺ as well as the support with Tb³⁺. In each case the nanocrystals and the lanthanide ions were immobilized at silica surface by impregnation procedure. Size of the ZnS quantum dots doped with Mn²⁺ were estimated by Scherrer method from the X-ray diffraction (XRD) pattern. The materials have been characterized by EPR and optical spectroscopy techniques. EPR spectra allow to distinguish two different Mn²⁺ sites: the first is assigned to isolated Mn²⁺ substitutionally and incorporated into cubic ZnS lattice and the second is ascribed to the Mn²⁺ situated near the nanocrystal surface. From the optical spectra we have found that in the three-component material, energy transfer from excited ZnS:Mn²⁺ nanocrystals to Tb³⁺ ions takes place. The different mechanisms of such transfer are discussed.     

Ion-acoustic shock waves with negative ions in presence of dust particulates

Dust acoustics shock waves have been investigated experimentally in a homogeneous unmagnetized dusty plasma device containing negative ions. When the negative ion density larger than a critical concentration ‘rc’ negative shock waves were observed instead of positive shock waves. Again when it is nearly equal to ‘rc’ both positive and negative shock waves propagate. The experimental findings are compared with modified KdV-Burgers equation. The velocity of the shock waves are also measured and compared with the numerical integration of modified KdV-Burgers equation.     

二次电子发射和负离子存在时的鞘层结构特性

建立了包括电子、离子、器壁发射二次电子以及负离子多种成分的等离子体无碰撞鞘层的基本模型,讨论了二次电子发射和负离子对1维稳态等离子体鞘层结构的影响,并且分析了多种成分等离子体鞘层内的二次电子和负离子的相互作用。结果表明：二次电子发射系数的增加和负离子含量的增加,都将导致鞘层的厚度有所减小;二次电子发射系数超过临界发射系数之后,鞘层不再是离子鞘。随着器壁材料二次电子发射系数的增加,鞘层中的负离子密度分布也逐渐增加;负离子的增加,导致二次电子临界发射系数有所增加。另外,在等离子体鞘层中二次电子发射和负离子的存在,也影响着鞘层中电子的放电特性与器壁材料的腐蚀。     

二次电子发射和负离子存在时的鞘层结构特性

 建立了包括电子、离子、器壁发射二次电子以及负离子多种成分的等离子体无碰撞鞘层的基本模型,讨论了二次电子发射和负离子对1维稳态等离子体鞘层结构的影响,并且分析了多种成分等离子体鞘层内的二次电子和负离子的相互作用。结果表明：二次电子发射系数的增加和负离子含量的增加,都将导致鞘层的厚度有所减小;二次电子发射系数超过临界发射系数之后,鞘层不再是离子鞘。随着器壁材料二次电子发射系数的增加,鞘层中的负离子密度分布也逐渐增加;负离子的增加,导致二次电子临界发射系数有所增加。另外,在等离子体鞘层中二次电子发射和负离子的存在,也影响着鞘层中电子的放电特性与器壁材料的腐蚀。