112 research outputs found
Stability of additive-free water-in-oil emulsions
We calculate ion distributions near a planar oil-water interface within
non-linear Poisson-Boltzmann theory, taking into account the Born self-energy
of the ions in the two media. For unequal self-energies of cations and anions,
a spontaneous charge separation is found such that the water and oil phase
become oppositely charged, in slabs with a typical thickness of the Debye
screening length in the two media. From the analytical solutions, the
corresponding interfacial charge density and the contribution to the
interfacial tension is derived, together with an estimate for the
Yukawa-potential between two spherical water droplets in oil. The parameter
regime is explored where the plasma coupling parameter exceeds the
crystallization threshold, i.e. where the droplets are expected to form
crystalline structures due to a strong Yukawa repulsion, as recently observed
experimentally. Extensions of the theory that we discuss briefly include
numerical calculations on spherical water droplets in oil, and analytical
calculations of the linear PB-equation for a finite oil-water interfacial
width.Comment: 9 pages, 4 figures, accepted by JPCM for proceedings of LMC
A Triangular Tessellation Scheme for the Adsorption Free Energy at the Liquid-Liquid Interface: Towards Non-Convex Patterned Colloids
We introduce a new numerical technique, namely triangular tessellation, to
calculate the free energy associated with the adsorption of a colloidal
particle at a flat interface. The theory and numerical scheme presented here
are sufficiently general to handle non-convex patchy colloids with arbitrary
surface patterns characterized by a wetting angle, e.g., amphiphilicity. We
ignore interfacial deformation due to capillary, electrostatic, or
gravitational forces, but the method can be extended to take such effects into
account. It is verified that the numerical method presented is accurate and
sufficiently stable to be applied to more general situations than presented in
this paper. The merits of the tessellation method prove to outweigh those of
traditionally used semi-analytic approaches, especially when it comes to
generality and applicability.Comment: 21 pages, 11 figures, 0 table
Self diffusion of particles in complex fluids: temporary cages and permanent barriers
We study the self diffusion of individual particles in dense (non-)uniform
complex fluids within dynamic density functional theory and explicitly account
for their coupling to the temporally fluctuating background particles. Applying
the formalism to rod-like particles in uniaxial nematic and smectic liquid
crystals, we find correlated diffusion in different directions: The temporary
cage formed by the neighboring particles competes with permanent barriers in
periodic inhomogeneous systems such as the lamellar smectic state and delays
self diffusion of particles even in uniform systems. We compare our theory with
recent experimental data on the self diffusion of fluorescently labelled
filamentous virus particles in aqueous dispersions in the smectic phase and
find qualitative agreement. This demonstrates the importance of explicitly
dealing with the time-dependent self-consistent molecular field that every
particle experiences.Comment: submitte
Spontaneous Charging and Crystallization of Water Droplets in Oil
We study the spontaneous charging and the crystallization of spherical
micron-sized water-droplets dispersed in oil by numerically solving, within a
Poisson-Boltzmann theory in the geometry of a spherical cell, for the density
profiles of the cations and anions in the system. We take into account
screening, ionic Born self-energy differences between oil and water, and
partitioning of ions over the two media. We find that the surface charge
density of the droplet as induced by the ion partitioning is significantly
affected by the droplet curvature and by the finite density of the droplets. We
also find that the salt concentration and the dielectric constant regime in
which crystallization of the water droplets is predicted is enhanced
substantially compared to results based on the planar oil-water interface,
thereby improving quantitative agreement with recent experiments.Comment: 10 pages, 7 figures, submitted for publicatio
Multiple packets of neutral molecules revolving for over a mile
The level of control that one has over neutral molecules in beams dictates
their possible applications. Here we experimentally demonstrate that
state-selected, neutral molecules can be kept together in a few mm long packet
for a distance of over one mile. This is accomplished in a circular arrangement
of 40 straight electrostatic hexapoles through which the molecules propagate
over 1000 times. Up to 19 packets of molecules have simultaneously been stored
in this ring structure. This brings the realization of a molecular low-energy
collider within reach
Orientational and phase-coexistence behaviour of hard rod-sphere mixtures
Results are presented from Monte Carlo simulations of bulk mixtures of Hard Gaussian Overlap particles with an aspect ratio of 3:1 and hard spheres with diameters equal to the breadths of the rods. For sphere number-concentrations of 50% and lower, compression of the isotropic fluid results in formation of a homogeneous (i.e. compositionally mixed) nematic phase. The volume fraction of this isotropic-nematic transition is found to increase approximately linearly with sphere concentration. On compression to higher volume fractions, however, this homogeneous nematic phase separates out into coexisting nematic and isotropic phases.</p
Nematic-Wetted Colloids in the Isotropic Phase: Pairwise Interaction, Biaxiality and Defects
We calculate the interaction between two spherical colloidal particles
embedded in the isotropic phase of a nematogenic liquid. The surface of the
particles induces wetting nematic coronas that mediate an elastic interaction.
In the weak wetting regime, we obtain exact results for the interaction energy
and the texture, showing that defects and biaxiality arise, although they are
not topologically required. We evidence rich behaviors, including the
possibility of reversible colloidal aggregation and dispersion. Complex
anisotropic self-assembled phases might be formed in dense suspensions.Comment: 4 pages, 6 figure
Assessing measurement invariance in the EORTC QLQ-C30
PURPOSE: We aimed to investigate measurement invariance (MI) in the European Organisation for research and treatment of cancer quality of life questionnaire core 30 (EORTC QLQ-C30) in a heterogeneous sample of patients with cancer. METHODS: Data from 12 studies within the PROFILES registry were used for secondary analyses (n = 7007). We tested MI by successive restrictions on thresholds, loadings, and intercepts across subgroups based on primary cancer sites, age, sex, time since diagnosis, and life stage, using multigroup confirmatory factor analysis (MGCFA) for ordered categorical measures. We also evaluated the impact of potentially miss-specified parameter equality across groups on latent factor means by releasing threshold and loading equality constraints for each item at a time. RESULTS: Results showed that the highest level of MI (invariance of thresholds, loadings, and intercepts) was found across groups based on time since diagnosis and life stage and to a lesser extent across groups based on sex, age, and primary tumor site. On item level, however, changes in the item’s associated factor means were relatively small and in most cases canceled each other out to some extent. CONCLUSIONS: Given only a few instances of non-invariance in our study, there is reason to be confident that valid conclusions can be drawn from between-group comparisons of QLQ-C30 latent means as operationalized in our study. Nonetheless, further research into MI between other subgroups for the QLQ-C30 (i.e., treatment effects and ethnicity) is warranted. We stress the importance of including MI evaluations in the development and validation of measurement instruments. SUPPLEMENTARY INFORMATION: The online version contains supplementary material available at 10.1007/s11136-021-02961-8
Effective Interactions and Volume Energies in Charged Colloids: Linear Response Theory
Interparticle interactions in charge-stabilized colloidal suspensions, of
arbitrary salt concentration, are described at the level of effective
interactions in an equivalent one-component system. Integrating out from the
partition function the degrees of freedom of all microions, and assuming linear
response to the macroion charges, general expressions are obtained for both an
effective electrostatic pair interaction and an associated microion volume
energy. For macroions with hard-sphere cores, the effective interaction is of
the DLVO screened-Coulomb form, but with a modified screening constant that
incorporates excluded volume effects. The volume energy -- a natural
consequence of the one-component reduction -- contributes to the total free
energy and can significantly influence thermodynamic properties in the limit of
low-salt concentration. As illustrations, the osmotic pressure and bulk modulus
are computed and compared with recent experimental measurements for deionized
suspensions. For macroions of sufficient charge and concentration, it is shown
that the counterions can act to soften or destabilize colloidal crystals.Comment: 14 pages, including 3 figure
Beware of density dependent pair potentials
Density (or state) dependent pair potentials arise naturally from
coarse-graining procedures in many areas of condensed matter science. However,
correctly using them to calculate physical properties of interest is subtle and
cannot be uncoupled from the route by which they were derived. Furthermore,
there is usually no unique way to coarse-grain to an effective pair potential.
Even for simple systems like liquid Argon, the pair potential that correctly
reproduces the pair structure will not generate the right virial pressure.
Ignoring these issues in naive applications of density dependent pair
potentials can lead to an apparent dependence of thermodynamic properties on
the ensemble within which they are calculated, as well as other
inconsistencies. These concepts are illustrated by several pedagogical
examples, including: effective pair potentials for systems with many-body
interactions, and the mapping of charged (Debye-H\"{u}ckel) and uncharged
(Asakura-Oosawa) two-component systems onto effective one-component ones.Comment: 22 pages, uses iopart.cls and iopart10.clo; submitted to Journal of
Physics Condensed Matter, special issue in honour of professor Jean-Pierre
Hanse
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