260 research outputs found
Coupling hydrophobic, dispersion, and electrostatic contributions in continuum solvent models
Recent studies of the hydration of micro- and nanoscale solutes have
demonstrated a strong {\it coupling} between hydrophobic, dispersion and
electrostatic contributions, a fact not accounted for in current implicit
solvent models. We present a theoretical formalism which accounts for coupling
by minimizing the Gibbs free energy with respect to a solvent volume exclusion
function. The solvent accessible surface is output of our theory. Our method is
illustrated with the hydration of alkane-assembled solutes on different length
scales, and captures the strong sensitivity to the particular form of the
solute-solvent interactions in agreement with recent computer simulations.Comment: 11 pages, 2 figure
Analytical modeling of micelle growth. 2. Molecular thermodynamics of mixed aggregates and scission energy in wormlike micelles
Hypotheses: Quantitative molecular-thermodynamic theory of the growth of
giant wormlike micelles in mixed nonionic surfactant solutions can be developed
on the basis of a generalized model, which includes the classical phase
separation and mass action models as special cases. The generalized model
describes spherocylindrical micelles, which are simultaneously multicomponent
and polydisperse in size. Theory: The model is based on explicit analytical
expressions for the four components of the free energy of mixed nonionic
micelles: interfacial-tension, headgroup-steric, chain-conformation components
and free energy of mixing. The radii of the cylindrical part and the spherical
endcaps, as well as the chemical composition of the endcaps, are determined by
minimization of the free energy. Findings: In the case of multicomponent
micelles, an additional term appears in the expression for the micelle growth
parameter (scission free energy), which takes into account the fact that the
micelle endcaps and cylindrical part have different compositions. The model
accurately predicts the mean mass aggregation number of wormlike micelles in
mixed nonionic surfactant solutions without using any adjustable parameters.
The endcaps are enriched in the surfactant with smaller packing parameter that
is better accommodated in regions of higher mean surface curvature. The model
can be further extended to mixed solutions of nonionic, ionic and zwitterionic
surfactants used in personal-care and house-hold detergency
Effective capillary interaction of spherical particles at fluid interfaces
We present a detailed analysis of the effective force between two smooth
spherical colloids floating at a fluid interface due to deformations of the
interface. The results hold in general and are applicable independently of the
source of the deformation provided the capillary deformations are small so that
a superposition approximation for the deformations is valid. We conclude that
an effective long--ranged attraction is possible if the net force on the system
does not vanish. Otherwise, the interaction is short--ranged and cannot be
computed reliably based on the superposition approximation. As an application,
we consider the case of like--charged, smooth nanoparticles and
electrostatically induced capillary deformation. The resulting long--ranged
capillary attraction can be easily tuned by a relatively small external
electrostatic field, but it cannot explain recent experimental observations of
attraction if these experimental systems were indeed isolated.Comment: 23 page
A mesoscopic model for microscale hydrodynamics and interfacial phenomena: Slip, films, and contact angle hysteresis
We present a model based on the lattice Boltzmann equation that is suitable
for the simulation of dynamic wetting. The model is capable of exhibiting
fundamental interfacial phenomena such as weak adsorption of fluid on the solid
substrate and the presence of a thin surface film within which a disjoining
pressure acts. Dynamics in this surface film, tightly coupled with
hydrodynamics in the fluid bulk, determine macroscopic properties of primary
interest: the hydrodynamic slip; the equilibrium contact angle; and the static
and dynamic hysteresis of the contact angles. The pseudo- potentials employed
for fluid-solid interactions are composed of a repulsive core and an attractive
tail that can be independently adjusted. This enables effective modification of
the functional form of the disjoining pressure so that one can vary the static
and dynamic hysteresis on surfaces that exhibit the same equilibrium contact
angle. The modeled solid-fluid interface is diffuse, represented by a wall
probability function which ultimately controls the momentum exchange between
solid and fluid phases. This approach allows us to effectively vary the slip
length for a given wettability (i.e. the static contact angle) of the solid
substrate
Analytical modeling of micelle growth. 3. Electrostatic free energy of ionic wormlike micelles -- effects of activity coefficients and spatially confined electric double layers
Hypotheses: To correctly predict the aggregation number and size of wormlike
micelles from ionic surfactants, the molecular-thermodynamic theory has to
calculate the free energy per molecule in the micelle with accuracy better than
0.01 kT, which is a serious challenge. The problem could be solved if the
effects of mutual confinement of micelle counterion atmospheres, as well as the
effects of counterion binding, surface curvature and ionic interactions in the
electric double layer (EDL), are accurately described. Theory: The electric
field is calculated using an appropriate cell model, which takes into account
the aforementioned effects. Expressions for the activity coefficients have been
used, which vary across the EDL and describe the electrostatic, hard sphere,
and specific interactions between the ions. New approach for fast numerical
calculation of the electrostatic free energy is developed. Findings: The
numerical results demonstrate the variation of quantities characterizing the
EDL of cylindrical and spherical micelles with the rise of electrolyte
concentration. The effect of activity coefficients leads to higher values of
the free energy per surfactant molecule in the micelle as compared with the
case of neglected ionic interactions. The results are essential for the correct
prediction of the size of wormlike micelles from ionic surfactants. This study
can be extended to mixed micelles of ionic and nonionic surfactants for
interpretation of the observed synergistic effects.Comment: 36 pages, 6 figures, Supplementary Information: 12 pages, 1 figur
Coupling nonpolar and polar solvation free energies in implicit solvent models
Recent studies on the solvation of atomistic and nanoscale solutes indicate
that a strong coupling exists between the hydrophobic, dispersion, and
electrostatic contributions to the solvation free energy, a facet not
considered in current implicit solvent models. We suggest a theoretical
formalism which accounts for coupling by minimizing the Gibbs free energy of
the solvent with respect to a solvent volume exclusion function. The resulting
differential equation is similar to the Laplace-Young equation for the
geometrical description of capillary interfaces, but is extended to microscopic
scales by explicitly considering curvature corrections as well as dispersion
and electrostatic contributions. Unlike existing implicit solvent approaches,
the solvent accessible surface is an output of our model. The presented
formalism is illustrated on spherically or cylindrically symmetrical systems of
neutral or charged solutes on different length scales. The results are in
agreement with computer simulations and, most importantly, demonstrate that our
method captures the strong sensitivity of solvent expulsion and dewetting to
the particular form of the solvent-solute interactions.Comment: accpted in J. Chem. Phy
Direct measurements of the effects of salt and surfactant on interaction forces between colloidal particles at water-oil interfaces
The forces between colloidal particles at a decane-water interface, in the
presence of low concentrations of a monovalent salt (NaCl) and of the
surfactant sodium dodecylsulfate (SDS) in the aqueous subphase, have been
studied using laser tweezers. In the absence of electrolyte and surfactant,
particle interactions exhibit a long-range repulsion, yet the variation of the
interaction for different particle pairs is found to be considerable. Averaging
over several particle pairs was hence found to be necessary to obtain reliable
assessment of the effects of salt and surfactant. It has previously been
suggested that the repulsion is consistent with electrostatic interactions
between a small number of dissociated charges in the oil phase, leading to a
decay with distance to the power -4 and an absence of any effect of electrolyte
concentration. However, the present work demonstrates that increasing the
electrolyte concentration does yield, on average, a reduction of the magnitude
of the interaction force with electrolyte concentration. This implies that
charges on the water side also contribute significantly to the electrostatic
interactions. An increase in the concentration of SDS leads to a similar
decrease of the interaction force. Moreover the repulsion at fixed SDS
concentrations decreases over longer times. Finally, measurements of three-body
interactions provide insight into the anisotropic nature of the interactions.
The unique time-dependent and anisotropic interactions between particles at the
oil-water interface allow tailoring of the aggregation kinetics and structure
of the suspension structure.Comment: Submitted to Langmui
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