Mean-field density functional theory of a nanoconfined classical, three-dimensional Heisenberg fluid. II. The interplay between molecular packing and orientational order

This article may be downloaded for personal use only. Any other use requires prior permission of the author and AIP Publishing. This article appeared in J. Chem. Phys. 149, 054704 (2018) and may be found at https://doi.org/10.1063/1.5040934.As in Paper I of this series of papers [S. M. Cattes et al., J. Chem. Phys. 144, 194704 (2016)], we study a Heisenberg fluid confined to a nanoscopic slit pore with smooth walls. The pore walls can either energetically discriminate specific orientations of the molecules next to them or are indifferent to molecular orientations. Unlike in Paper I, we employ a version of classical density functional theory that allows us to explicitly account for the stratification of the fluid (i.e., the formation of molecular layers) as a consequence of the symmetry-breaking presence of the pore walls. We treat this stratification within the White Bear version (Mark I) of fundamental measure theory. Thus, in this work, we focus on the interplay between local packing of the molecules and orientational features. In particular, we demonstrate why a critical end point can only exist if the pore walls are not energetically discriminating specific molecular orientations. We analyze in detail the positional and orientational order of the confined fluid and show that reorienting molecules across the pore space can be a two-dimensional process. Last but not least, we propose an algorithm based upon a series expansion of Bessel functions of the first kind with which we can solve certain types of integrals in a very efficient manner.DFG, 65143814, GRK 1524: Self-Assembled Soft-Matter Nanostructures at Interface

Selectivity in binary fluid mixtures: static and dynamical properties

Selectivity of particles in a region of space can be achieved by applying external potentials to influence the particles in that region. We investigate static and dynamical properties of size selectivity in binary fluid mixtures of two particles sizes. We find that by applying an external potential that is attractive to both kinds of particles, due to crowding effects, this can lead to one species of particles being expelled from that region, whilst the other species is attracted into the region where the potential is applied. This selectivity of one species of particle over the other in a localized region of space depends on the density and composition of the fluid mixture. Applying an external potential that repels both kinds of particles leads to selectivity of the opposite species of particles to the selectivity with attractive potentials. We use equilibrium and dynamical density functional theory to describe and understand the static and dynamical properties of this striking phenomenon. Selectivity by some ion-channels is believed to be due to this effect.Comment: 11 pages, 9 figure

On the Physics of Size Selectivity

We demonstrate that two mechanisms used by biological ion channels to select particles by size are driven by entropy. With uncharged particles in an infinite cylinder, we show that a channel that attracts particles is small-particle selective and that a channel that repels water from the wall is large-particle selective. Comparing against extensive density-functional theory calculations of our model, we find that the main physics can be understood with surprisingly simple bulk models that neglect the confining geometry of the channel completely.Comment: 4 pages, 3 figures, Phys. Rev. Lett. (accepted

Hypernuclear No-Core Shell Model

We extend the No-Core Shell Model (NCSM) methodology to incorporate strangeness degrees of freedom and apply it to single-$\Lambda$ hypernuclei. After discussing the transformation of the hyperon-nucleon (YN) interaction into Harmonic-Oscillator (HO) basis and the Similarity Renormalization Group transformation applied to it to improve model-space convergence, we present two complementary formulations of the NCSM, one that uses relative Jacobi coordinates and symmetry-adapted basis states to fully exploit the symmetries of the hypernuclear Hamiltonian, and one working in a Slater determinant basis of HO states where antisymmetrization and computation of matrix elements is simple and to which an importance-truncation scheme can be applied. For the Jacobi-coordinate formulation, we give an iterative procedure for the construction of the antisymmetric basis for arbitrary particle number and present the formulae used to embed two- and three-baryon interactions into the many-body space. For the Slater-determinant formulation, we discuss the conversion of the YN interaction matrix elements from relative to single-particle coordinates, the importance-truncation scheme that tailors the model space to the description of the low-lying spectrum, and the role of the redundant center-of-mass degrees of freedom. We conclude with a validation of both formulations in the four-body system, giving converged ground-state energies for a chiral Hamiltonian, and present a short survey of the $A\le7$ hyper-helium isotopes.Comment: 17 pages, 8 figures; accepted versio

Morphometric approach to many-body correlations in hard spheres

We model the thermodynamics of local structures within the hard sphere liquid at arbitrary volume fractions through the \textit{morphometric} calculation of $n$-body correlations. We calculate absolute free energies of local geometric motifs in excellent quantitative agreement with molecular dynamics simulations across the liquid and supercooled liquid regimes. We find a bimodality in the density library of states where five-fold symmetric structures appear lower in free energy than four-fold symmetric structures, and from a single reaction path predict a relaxation barrier which scales linearly in the compressibility factor. The method provides a new route to assess changes in the free energy landscape at volume fractions dynamically inaccessible to conventional techniques.Comment: 6+17 pages, 3 figure

Ab Initio Description of p-Shell Hypernuclei

We present the first ab initio calculations for p-shell single-Lambda hypernuclei. For the solution of the many-baryon problem, we develop two variants of the no-core shell model with explicit $\Lambda$ and $\Sigma^+$, $\Sigma^0$, $\Sigma^-$ hyperons including $\Lambda$-$\Sigma$ conversion, optionally supplemented by a similarity renormalization group transformation to accelerate model-space convergence. In addition to state-of-the-art chiral two- and three-nucleon interactions, we use leading-order chiral hyperon-nucleon interactions and a recent meson-exchange hyperon-nucleon interaction. We validate the approach for s-shell hypernuclei and apply it to p-shell hypernuclei, in particular to $^7_\Lambda$Li, $^9_\Lambda$Be and $^{13}_\Lambda$C. We show that the chiral hyperon-nucleon interactions provide ground-state and excitation energies that agree with experiment within the cutoff dependence. At the same time we demonstrate that hypernuclear spectroscopy provides tight constraints on the hyperon-nucleon interactions and we discuss the impact of induced hyperon-nucleon-nucleon interactions.Comment: 6 pages, 4 figure

Density functional theory for hard-sphere mixtures: the White-Bear version Mark II

In the spirit of the White-Bear version of fundamental measure theory we derive a new density functional for hard-sphere mixtures which is based on a recent mixture extension of the Carnahan-Starling equation of state. In addition to the capability to predict inhomogeneous density distributions very accurately, like the original White-Bear version, the new functional improves upon consistency with an exact scaled-particle theory relation in the case of the pure fluid. We examine consistency in detail within the context of morphological thermodynamics. Interestingly, for the pure fluid the degree of consistency of the new version is not only higher than for the original White-Bear version but also higher than for Rosenfeld's original fundamental measure theory.Comment: 16 pages, 3 figures; minor changes; J. Phys.: Condens. Matter, accepte

Predicting metapopulation responses to conservation in human-dominated landscapes

Loss of habitat to urbanization is a primary cause of population declines as human-dominated landscapes expand at increasing rates. Understanding how the relative effects of different conservation strategies is important to slow population declines for species in urban landscapes. We studied the wood thrush Hylocichla mustelina, a declining forest-breeding Neotropical migratory species, and umbrella species for forest-breeding songbirds, within the urbanized mid-Atlantic United States. We integrated 40 years of demographic data with contemporary metapopulation model simulations of breeding wood thrushes to predict population responses to differing conservation scenarios. We compared four conservation scenarios over a 30-year time period (2014-2044) representing (A) current observed state (Null), (B) replacing impervious surface with forest (Reforest), (C) reducing brown-headed cowbird Molothrus ater parasitism pressure (Cowbird removal), and (D) simultaneous reforesting and cowbird removal. Compared to the Null scenario, the Reforest scenario increased mean annual population trends by 54%, the Remove cowbirds scenario increased mean annual population trends by 38%, and the scenario combining reforestation and cowbird removal increased mean annual population trends by 98%. Mean annual growth rates (lambda) per site were greater in the Reforest (lambda = 0.94) and Remove cowbirds (lambda = 0.92) compared to the Null (lambda = 0.88) model scenarios. However, only by combining the positive effects of reforestation and cowbird removal did wood thrush populations stop declining (lambda = 1.00). Our results suggest that independently replacing impervious surface with forest habitat around forest patches and removing cowbirds may slow current negative population trends. Furthermore, conservation efforts that combine reforestation and cowbird removal may potentially benefit populations of wood thrushes and other similarly forest-breeding songbird species within urbanized fragmented landscapes that typify the mid-Atlantic United States

Polyhedral colloidal `rocks': low-dimensional networks

We introduce a model system of anisotropic colloidal `rocks'. Due to their shape, the bonding introduced via non-absorbing polymers is profoundly different from spherical particles: bonds between rocks are rigid against rotation, leading to strong frustration. We develop a geometric model which captures the essence of the rocks. Experiments and simulations show that the colloid geometry leads to structures of low fractal dimension. This is in stark contrast to gels of spheres, whose rigidity results from locally dense regions. At high density the rocks form a quasi one-component glass