Criticality in Charge-asymmetric Hard-sphere Ionic Fluids

Phase separation and criticality are analyzed in $z$:1 charge-asymmetric ionic fluids of equisized hard spheres by generalizing the Debye-H\"{u}ckel approach combined with ionic association, cluster solvation by charged ions, and hard-core interactions, following lines developed by Fisher and Levin (1993, 1996) for the 1:1 case (i.e., the restricted primitive model). Explicit analytical calculations for 2:1 and 3:1 systems account for ionic association into dimers, trimers, and tetramers and subsequent multipolar cluster solvation. The reduced critical temperatures, $T_c^*$ (normalized by $z$), \textit{decrease} with charge asymmetry, while the critical densities \textit{increase} rapidly with $z$. The results compare favorably with simulations and represent a distinct improvement over all current theories such as the MSA, SPB, etc. For $z$$\ne$1, the interphase Galvani (or absolute electrostatic) potential difference, $\Delta \phi(T)$, between coexisting liquid and vapor phases is calculated and found to vanish as $|T-T_c|^\beta$ when $T\to T_c-$ with, since our approximations are classical, $\beta={1/2}$. Above $T_c$, the compressibility maxima and so-called $k$-inflection loci (which aid the fast and accurate determination of the critical parameters) are found to exhibit a strong $z$-dependence.Comment: 25 pages, 14 figures; last update with typos corrected and some added reference

On the Stability of Electrostatic Orbits

We analyze the stability of two charged conducting spheres orbiting each other. Due to charge polarization, the electrostatic force between the two spheres deviates significantly from $1/r^2$ as they come close to each other. As a consequence, there exists a critical angular momentum, $L_c$, with a corresponding critical radius $r_c$. For $L > L_c$ two circular orbits are possible: one at $r > r_c$ that is stable and the other at $r < r_c$ that is unstable. This critical behavior is analyzed as a function of the charge and the size ratios of the two spheres.Comment: Added references, corrected typos, clarified languag

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

Computation of Lipid Headgroup Interactions

The equilibrium structure of lipid aggregates is determined by the balance of numerous forces between hydrophobic acyl chains, hydrophilic lipid headgroups, and the lipid\u27s environment. Among these forces, lipid headgroup interactions are both important to the stability of lipid structures and responsible for many of the interactions between biological membranes and aqueous solutes including ions and soluble peptides. In order to model these headgroup interactions, we consider the electrical properties of the headgroup molecules via the multipole expansion. While common lipid headgroups such as phosphatidylcholine are electrically neutral, they are characterized by non-zero higher order terms in the multipole expansion. Making a dipole approximation, we employ a two dimensional lattice of classical dipoles to model the headgroup networks of lipid aggregates. Restrictions to each dipole\u27s position and orientation are imposed to account for the effect of hydrocarbon chains which are not included in the model. A Monte Carlo algorithm is used to calculate headgroup-headgroup interactions and network energies in both dipole and point-charge approximations