RESUMEN
Using the Lennard-Jones potential, we determine analytical expressions for van der Waals interaction energies between a point and a rectangular prism-shaped pore, writing them in terms of standard elementary functions. The parameter values for a new ferric ion sensor are used to compare these calculations with the cylindrical pore approximation for the interactions between an ion and a metal organic framework (MOF) pore. The results using the prismatic pore approximation predict the same qualitative outcomes as a cylindrical pore approximation. However, the prismatic approximation predicts lower magnitudes for both the interaction potential energy minimum and the force maximum, since the average distance from the centre-line to the surface of the prism is greater. We suggest that in some circumstances it is sufficient to use the simpler cylindrical approximation, provided that the cylinder radius is chosen so that the cross-sectional area is equal to the area of the prism pore opening. However, atoms at the nodes should remain approximated by semi-infinite lines. We also determine the interaction between a second ferric ion and a blocked MOF pore; as expected, the second ferric ion experiences a force away from the pore, implying that approaching ferric ions can only occupy vacant MOF pores.
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We consider coupled systems of advection-diffusion equations with initial and boundary conditions and determine conditions on the advection terms that allow us to obtain solutions that can be explicitly bounded above and below using the initial and boundary conditions. Given the advection terms, using our methodology one can easily check if such bounds can be obtained and then one can construct the necessary nonlinear transformation to allow the bounds to be determined. We apply this technique to determine bounding quantities for a number of examples. In particular, we show that the three-ion electroneutral Poisson-Nernst-Planck system of equations can be transformed into a system, which allows for the use of our techniques and we determine the bounding quantities. In addition, we determine the general form of advection terms that allow these techniques to be applied and show that our method can be applied to a very wide class of advection-diffusion equations.
RESUMEN
Motivated by several biological models such as the SIS model from epidemiology and the Tuckwell-Miura model describing cortical spreading depression, we investigate the types of wave solutions that can exist for reaction-diffusion systems of two equations in which the reaction terms are degenerate in the sense that they are linearly dependent. In particular, we show that there are surprising differences between the types of waves that occur in a single reaction-diffusion equation and the types of waves that occur in a degenerate system of two equations. Importantly, and in contrast to previously published results, we demonstrate that nonstationary pulse solutions can exist for a degenerate system of two equations but cannot exist for a single reaction-diffusion equation. We show that this has important consequences for the minimal model that can generate the types of waves observed in cortical spreading depression. On the other hand, stationary fronts can exist for both single reaction-diffusion equations and degenerate systems. However, for degenerate systems, such solutions cannot be accessed when perturbing a uniform rest state with a localized perturbation unless the diffusion coefficients of the two species are equal. We also give an explicit condition on the source term in a degenerate reaction-diffusion system that guarantees the existence of nonstationary and stationary pulse and front solutions. We use this approach to provide several examples of reaction terms that have analytical pulse and front solutions. We also show that the case in which one species cannot diffuse is singular in the sense that the degenerate reaction-diffusion system can admit infinite families of stationary piecewise constant solutions. We further show how such solutions can be accessed by perturbing a constant rest state with a localized continuous disturbance.
RESUMEN
In this paper, we present a theoretical analysis of the dielectric response of a dense suspension of spherical colloidal particles based on a self-consistent cell model. Particular attention is paid to (a) the relationship between the dielectric response and the conductivity response and (b) the connection between the real and imaginary parts of these responses based on the Kramers-Kronig relations. We have thus clarified the analysis of Carrique et al. (Carrique, F.; Criado, C.; Delgado, A. V. J. Colloid Interface Sci. 1993, 156, 117). We have shown that both the conduction and displacement current components are complex quantities with both real and imaginary parts being frequency dependent. The dielectric response exhibits characteristics of two relaxation phenomena: the Maxwell-Wagner and the alpha-relaxations, with the imaginary part being the more sensitive instrument. The inverse Fourier transform of the simulated dielectric response is compared with a phenomenological, two-exponential response function with good agreement obtained. The two fitted decay times also compare well with times extracted from the explicit simulations.
RESUMEN
A matched asymptotic analysis of the system of equations governing the electrokinetic cell model of ref 4 (Ahualli, S.; Delgado, A.; Miklavcic, S.; White, L. R. Langmuir 2006, 22, 7041) is performed. Asymptotic expressions are obtained for the dynamic mobility and complex conductivity response of a dense suspension of charged spherical particles to an applied electric field. The asymptotic expressions are compared with full numerical calculations of the linear response functions as a function of surface (zeta) potential, electrolyte strength, and particle density. We find that the numerical procedure used is robust and highly accurate at a very high frequency under a wide range of double-layer conditions. The asymptotic form for the dielectric response of the system is accurate to megahertz frequencies. The asymptotic formulas for the other response functions have limited viability as predictive tools within the current range of experimentally accessible frequencies but are useful as checks on numerical calculations.
RESUMEN
The cell-model electrokinetic theory of Ahualli et al. Langmuir 2006, 22, 7041; Ahualli et al. J. Colloid Interface Sci. 2007, 309, 342; and Bradshaw-Hajek et al. Langmuir 2008, 24, 4512 is applied to a dense suspension of charged spherical particles, to exhibit the system's dielectric response to an applied electric field as a function of solids volume fraction. The model's predictions of effective permittivity and complex conductivity are favorably compared with published theoretical calculations and experimental measurements on dense colloidal systems. Physical factors governing the volume fraction dependence of the dielectric response are discussed.
RESUMEN
This paper outlines the application of a self-consistent cell-model theory of electrokinetics to the problem of determining the electrical conductivity of a dense suspension of spherical colloidal particles. Numerical solutions of the standard electrokinetic equations, subject to self-consistent boundary conditions, are implemented in formulas for the electrical conductivity appropriate to the particle-averaged cell model of the suspension. Results of calculations as a function of frequency, zeta potential, volume fraction, and electrolyte composition, are presented and discussed.