The Poisson-Boltzmann model for implicit solvation of electrolyte solutions: Quantum chemical implementation and assessment via Sechenov coefficients.

We present the theory and implementation of a Poisson-Boltzmann implicit solvation model for electrolyte solutions. This model can be combined with arbitrary electronic structure methods that provide an accurate charge density of the solute. A hierarchy of approximations for this model includes a linear approximation for weak electrostatic potentials, finite size of the mobile electrolyte ions, and a Stern-layer correction. Recasting the Poisson-Boltzmann equations into Euler-Lagrange equations then significantly simplifies the derivation of the free energy of solvation for these approximate models. The parameters of the model are either fit directly to experimental observables-e.g., the finite ion size-or optimized for agreement with experimental results. Experimental data for this optimization are available in the form of Sechenov coefficients that describe the linear dependence of the salting-out effect of solutes with respect to the electrolyte concentration. In the final part, we rationalize the qualitative disagreement of the finite ion size modification to the Poisson-Boltzmann model with experimental observations by taking into account the electrolyte concentration dependence of the Stern layer. A route toward a revised model that captures the experimental observations while including the finite ion size effects is then outlined. This implementation paves the way for the study of electrochemical and electrocatalytic processes of molecules and cluster models with accurate electronic structure methods

Global surface slopes and roughness of the Moon from the Lunar Orbiter Laser Altimeter

The acquisition of new global elevation data from the Lunar Orbiter Laser Altimeter, carried on the Lunar Reconnaissance Orbiter, permits quantification of the surface roughness properties of the Moon at unprecedented scales and resolution. We map lunar surface roughness using a range of parameters: median absolute slope, both directional (along-track) and bidirectional (in two dimensions); median differential slope; and Hurst exponent, over baselines ranging from ~17 m to ~2.7 km. We find that the lunar highlands and the mare plains show vastly different roughness properties, with subtler variations within mare and highlands. Most of the surface exhibits fractal-like behavior, with a single or two different Hurst exponents over the given baseline range; when a transition exists, it typically occurs near the 1 km baseline, indicating a significant characteristic spatial scale for competing surface processes. The Hurst exponent is high within the lunar highlands, with a median value of 0.95, and lower in the maria (with a median value of 0.76). The median differential slope is a powerful tool for discriminating between roughness units and is useful in characterizing, among other things, the ejecta surrounding large basins, particularly Orientale, as well as the ray systems surrounding young, Copernican-age craters. In addition, it allows a quantitative exploration on mare surfaces of the evolution of surface roughness with age

Unfolding cross-linkers as rheology regulators in F-actin networks

We report on the nonlinear mechanical properties of a statistically homogeneous, isotropic semiflexible network cross-linked by polymers containing numerous small unfolding domains, such as the ubiquitous F-actin cross-linker Filamin. We show that the inclusion of such proteins has a dramatic effect on the large strain behavior of the network. Beyond a strain threshold, which depends on network density, the unfolding of protein domains leads to bulk shear softening. Past this critical strain, the network spontaneously organizes itself so that an appreciable fraction of the Filamin cross-linkers are at the threshold of domain unfolding. We discuss via a simple mean-field model the cause of this network organization and suggest that it may be the source of power-law relaxation observed in in vitro and in intracellular microrheology experiments. We present data which fully justifies our model for a simplified network architecture.Comment: 11 pages, 4 figures. to appear in Physical Review

Transverse fluctuations of grafted polymers

We study the statistical mechanics of grafted polymers of arbitrary stiffness in a two-dimensional embedding space with Monte Carlo simulations. The probability distribution function of the free end is found to be highly anisotropic and non-Gaussian for typical semiflexible polymers. The reduced distribution in the transverse direction, a Gaussian in the stiff and flexible limits, shows a double peak structure at intermediate stiffnesses. We also explore the response to a transverse force applied at the polymer free end. We identify F-Actin as an ideal benchmark for the effects discussed.Comment: 10 pages, 4 figures, submitted to Physical Review

Cardiovascular disease in a cohort exposed to the 1940-45 Channel Islands occupation

BACKGROUND To clarify the nature of the relationship between food deprivation/undernutrition during pre- and postnatal development and cardiovascular disease (CVD) in later life, this study examined the relationship between birth weight (as a marker of prenatal nutrition) and the incidence of hospital admissions for CVD from 1997–2005 amongst 873 Guernsey islanders (born in 1923–1937), 225 of whom had been exposed to food deprivation as children, adolescents or young adults (i.e. postnatal undernutrition) during the 1940–45 German occupation of the Channel Islands, and 648 of whom had left or been evacuated from the islands before the occupation began. METHODS Three sets of Cox regression models were used to investigate (A) the relationship between birth weight and CVD, (B) the relationship between postnatal exposure to the occupation and CVD and (C) any interaction between birth weight, postnatal exposure to the occupation and CVD. These models also tested for any interactions between birth weight and sex, and postnatal exposure to the occupation and parish of residence at birth (as a marker of parish residence during the occupation and related variation in the severity of food deprivation). RESULTS The first set of models (A) found no relationship between birth weight and CVD even after adjustment for potential confounders (hazard ratio (HR) per kg increase in birth weight: 1.12; 95% confidence intervals (CI): 0.70 – 1.78), and there was no significant interaction between birth weight and sex (p = 0.60). The second set of models (B) found a significant relationship between postnatal exposure to the occupation and CVD after adjustment for potential confounders (HR for exposed vs. unexposed group: 2.52; 95% CI: 1.54 – 4.13), as well as a significant interaction between postnatal exposure to the occupation and parish of residence at birth (p = 0.01), such that those born in urban parishes (where food deprivation was worst) had a greater HR for CVD than those born in rural parishes. The third model (C) found no interaction between birth weight and exposure to the occupation (p = 0.43). CONCLUSION These findings suggest that the levels of postnatal undernutrition experienced by children, adolescents and young adults exposed to food deprivation during the 1940–45 occupation of the Channel Islands were a more important determinant of CVD in later life than the levels of prenatal undernutrition experienced in utero prior to the occupatio

Slowly driven sandpile formation with granular mixtures

We introduce a one-dimensional sandpile model with $N$ different particle types and an infinitesimal driving rate. The parameters for the model are the N^2 critical slopes for one type of particle on top of another. The model is trivial when N=1, but for N=2 we observe four broad classes of sandpile structure in different regions of the parameter space. We describe and explain the behaviour of each of these classes, giving quantitative analysis wherever possible. The behaviour of sandpiles with N>2 essentially consists of combinations of these four classes. We investigate the model's robustness and highlight the key areas that any experiment designed to reproduce these results should focus on

A microscopic 2D lattice model of dimer granular compaction with friction

We study by Monte Carlo simulation the compaction dynamics of hard dimers in 2D under the action of gravity, subjected to vertical and horizontal shaking, considering also the case in which a friction force acts for horizontal displacements of the dimers. These forces are modeled by introducing effective probabilities for all kinds of moves of the particles. We analyze the dynamics for different values of the time $\tau$ during which the shaking is applied to the system and for different intensities of the forces. It turns out that the density evolution in time follows a stretched exponential behavior if $\tau$ is not very large, while a power law tail develops for larger values of $\tau$. Moreover, in the absence of friction, a critical value $\tau^*$ exists which signals the crossover between two different regimes: for $\tau < \tau^*$ the asymptotic density scales with a power law of $\tau$, while for $\tau > \tau^*$ it reaches logarithmically a maximal saturation value. Such behavior smears out when a finite friction force is present. In this situation the dynamics is slower and lower asymptotic densities are attained. In particular, for significant friction forces, the final density decreases linearly with the friction coefficient. We also compare the frictionless single tap dynamics to the sequential tapping dynamics, observing in the latter case an inverse logarithmic behavior of the density evolution, as found in the experiments.Comment: 10 pages, 15 figures, to be published in Phys. Rev.

Stress Transmission through Three-Dimensional Ordered Granular Arrays

We measure the local contact forces at both the top and bottom boundaries of three-dimensional face-centered-cubic and hexagonal-close-packed granular crystals in response to an external force applied to a small area at the top surface. Depending on the crystal structure, we find markedly different results which can be understood in terms of force balance considerations in the specific geometry of the crystal. Small amounts of disorder are found to create additional structure at both the top and bottom surfaces.Comment: 9 pages including 9 figures (many in color) submitted to PR

The jamming transition of Granular Media

We briefly review the basics ideas and results of a recently proposed statistical mechanical approach to granular materials. Using lattice models from standard Statistical Mechanics and results from a mean field replica approach and Monte Carlo simulations we find a jamming transition in granular media closely related to the glass transition in super-cooled liquids. These models reproduce the logarithmic relaxation in granular compaction and reversible-irreversible lines, in agreement with experimental data. The models also exhibit aging effects and breakdown of the usual fluctuation dissipation relation. It is shown that the glass transition may be responsible for the logarithmic relaxation and may be related to the cooperative effects underlying many phenomena of granular materials such as the Reynolds transition.Comment: 18 pages with 6 postscript figures. to appear in J.Phys: Cond. Ma

Entanglement Measures for Single- and Multi-Reference Correlation Effects

Electron correlation effects are essential for an accurate ab initio description of molecules. A quantitative a priori knowledge of the single- or multi-reference nature of electronic structures as well as of the dominant contributions to the correlation energy can facilitate the decision regarding the optimum quantum chemical method of choice. We propose concepts from quantum information theory as orbital entanglement measures that allow us to evaluate the single- and multi-reference character of any molecular structure in a given orbital basis set. By studying these measures we can detect possible artifacts of small active spaces.Comment: 14 pages, 4 figure