Charge reversal and surface charge amplification in asymmetric valence restricted primitive model planar electric double layers in the modified Poisson-Boltzmann theory

The modified Poisson-Boltzmann theory of the restricted primitive model double layer is revisited and recast in a fresh, slightly broader perspective. Derivation of relevant equations follow the techniques utilized in the earlier MPB4 and MPB5 formulations and clarifies the relationship between these. The MPB4, MPB5, and a new formulation of the theory are employed in an analysis of the structure and charge reversal phenomenon in asymmetric 2:1/1:2 valence electrolytes. Furthermore, polarization induced surface charge amplification is studied in 3:1/1:3 systems. The results are compared to the corresponding Monte Carlo simulations. The theories are seen to predict the "exact" simulation data to varying degrees of accuracy ranging from qualitative to almost quantitative. The results from a new version of the theory are found to be of comparable accuracy as the MPB5 results in many situations. However, in some cases involving low electrolyte concentrations, theoretical artifacts in the form of un-physical "shoulders" in the singlet ionic distribution functions are observed.Comment: 15 pages, 13 figure

Electrostatic Field Classifier for Deficient Data

This paper investigates the suitability of recently developed models based on the physical field phenomena for classification problems with incomplete datasets. An original approach to exploiting incomplete training data with missing features and labels, involving extensive use of electrostatic charge analogy, has been proposed. Classification of incomplete patterns has been investigated using a local dimensionality reduction technique, which aims at exploiting all available information rather than trying to estimate the missing values. The performance of all proposed methods has been tested on a number of benchmark datasets for a wide range of missing data scenarios and compared to the performance of some standard techniques. Several modifications of the original electrostatic field classifier aiming at improving speed and robustness in higher dimensional spaces are also discussed

Thermodynamics of primitive model electrolytes in the symmetric and modified Poisson-Boltzmann theories. A comparative study with Monte Carlo simulations

Osmotic coefficients, individual and mean activity coefficients of primitive model electrolyte solutions are computed at different molar concentrations using the symmetric Poisson-Boltzmann and modified Poisson-Boltzmann theories. The theoretical results are compared with an extensive series of Monte Carlo simulation data obtained by Abbas et al. [Fluid Phase Equilib., 2007, 260, 233; J. Phys. Chem. B, 2009, 113, 5905]. The agreement between modified Poisson-Boltzmann predictions with the "exact" simulation results is almost quantitative for monovalent salts, while being semi-quantitative or better for higher and multivalent salts. The symmetric Poisson-Boltzmann results, on the other hand, are very good for monovalent systems but tend to deviate at higher concentrations and/or for multi-valent systems. Some recent experimental values for activity coefficients of HCl solution (individual and mean activities) and NaCl solution (mean activity only) have also been compared with the symmetric and modified Poisson-Boltzmann theories, and with the Monte Carlo simulations.Comment: 10 pages, 9 figure

How Multivalency controls Ionic Criticality

To understand how multivalency influences the reduced critical temperatures, Tce (z), and densities, roce (z), of z : 1 ionic fluids, we study equisized hard-sphere models with z = 1-3. Following Debye, Hueckel and Bjerrum, association into ion clusters is treated with, also, ionic solvation and excluded volume. In good accord with simulations but contradicting integral-equation and field theories, Tce falls when z increases while roce rises steeply: that 80-90% of the ions are bound in clusters near T_c serves to explain these trends. For z \neq 1 interphase Galvani potentials arise and are evaluated.Comment: 4 pages, 4 figure

The primitive model of ionic fluids near its critical point in the Poisson–Boltzmann and modified Poisson–Boltzmann theories

The Poisson–Boltzmann (PB) and modified Poisson–Boltzmann (MPB) theories are used to investigate the primitive model of ionic fluids in the low density–large coupling regime where the liquid–vapor transition is situated. The PB and MPB spinodal curves for the restricted primitive model are calculated from the virial route and compared with those from the mean spherical approximation (energy route) and the hybrid hypernetted‐chain/mean spherical approximation (virial route). The effect of unequal ion sizes on the critical point and spinodal curves is also considered.National Sanitation Foundation (NSF) EE.UU. CHE-8907130Fondo Institucional para la Investigación (FIPI) de la Universidad de Puerto RicoComunidad Europea (beca Marie Curie)Dirección General de Investigación Científica y Técnica (DGICYT). España PBgl / 060

Mesoscopic theory for size- and charge- asymmetric ionic systems. I. Case of extreme asymmetry

A mesoscopic theory for the primitive model of ionic systems is developed for arbitrary size, $\lambda=\sigma_+/\sigma_-$, and charge, $Z=e_+/|e_-|$, asymmetry. Our theory is an extension of the theory we developed earlier for the restricted primitive model. The case of extreme asymmetries $\lambda\to\infty$ and $Z \to\infty$ is studied in some detail in a mean-field approximation. The phase diagram and correlation functions are obtained in the asymptotic regime $\lambda\to\infty$ and $Z \to\infty$, and for infinite dilution of the larger ions (volume fraction $n_p\sim 1/Z$ or less). We find a coexistence between a very dilute 'gas' phase and a crystalline phase in which the macroions form a bcc structure with the lattice constant $\approx 3.6\sigma_+$. Such coexistence was observed experimentally in deionized aqueous solutions of highly charged colloidal particles

The Urgency of Critical Theory Today: Towards Optimism and Renewal in a Neoliberal World

This article takes the form of a critical conversation between three generations of critical theorists, examining the role of critical theory in the neoliberal academy: does this sort of intellectual project still have a place in an academic and educational system that tends to favour empirical research and policy-driven projects? Through a discussion of the relationship between critical theory and power, privilege, and positionality, the article addresses the ongoing urgency of such intellectual activities in the present context. The dialogue between the three participants acknowledges critical theory’s historical, and continuing, fragility within the university, while elucidating the ways that it can provide a vehicle for challenging dominant forms of power. In doing so, this cross-generational exchange demonstrates that critical theory remains a vital space of rebellion, optimism, and social change