arXiv subjects

A. R. Denton

Publications and source records attributed to A. R. Denton.

14 recordsLinked to original sources

arXiv2007

Electroneutrality and Phase Behavior of Colloidal Suspensions

Several statistical mechanical theories predict that colloidal suspensions of highly charged macroions and monovalent microions can exhibit unusual thermodynamic phase behavior when strongly deionized. Density-functional, extended Debye-Hückel, and response theories, within mean-field and linearization approximations, predict a spinodal phase instability of charged colloids below a critical salt concentration. Poisson-Boltzmann cell model studies of suspensions in Donnan equilibrium with a salt reservoir demonstrate that effective interactions and osmotic pressures predicted by such theories can be sensitive to the choice of reference system, e.g., whether the microion density profiles are expanded about the average potential of the suspension or about the reservoir potential. By unifying Poisson-Boltzmann and response theories within a common perturbative framework, it is shown here that the choice of reference system is dictated by the constraint of global electroneutrality. On this basis, bulk suspensions are best modeled by density-dependent effective interactions derived from a closed reference system in which the counterions are confined to the same volume as the macroions. Linearized theories then predict bulk phase separation of deionized suspensions only when expanded about a physically consistent (closed) reference system. Lower-dimensional systems (e.g., monolayers, small clusters), depending on the strength of macroion-counterion correlations, may be governed instead by density-independent effective interactions tied to an open reference system with counterions dispersed throughout the reservoir, possibly explaining observed structural crossover in colloidal monolayers and anomalous metastability of colloidal crystallites.

cond-mat.soft↗

arXiv2004

Nonlinear Screening and Effective Electrostatic Interactions in Charge-Stabilized Colloidal Suspensions

A nonlinear response theory is developed and applied to electrostatic interactions between spherical macroions, screened by surrounding microions, in charge-stabilized colloidal suspensions. The theory describes leading-order nonlinear response of the microions (counterions, salt ions) to the electrostatic potential of the macroions and predicts microion-induced effective many-body interactions between macroions. A linear response approximation [Phys. Rev. E 62, 3855 (2000)] yields an effective pair potential of screened-Coulomb (Yukawa) form, as well as a one-body volume energy, which contributes to the free energy. Nonlinear response generates effective many-body interactions and essential corrections to both the effective pair potential and the volume energy. By adopting a random-phase approximation (RPA) for the response functions, and thus neglecting microion correlations, practical expressions are derived for the effective pair and triplet potentials and for the volume energy. Nonlinear screening is found to weaken repulsive pair interactions, induce attractive triplet interactions, and modify the volume energy. Numerical results for monovalent microions are in good agreement with available ab initio simulation data and demonstrate that nonlinear effects grow with increasing macroion charge and concentration and with decreasing salt concentration. In the dilute limit of zero macroion concentration, leading-order nonlinear corrections vanish. Finally, it is shown that nonlinear response theory, when combined with the RPA, is formally equivalent to the mean-field Poisson-Boltzmann theory and that the linear response approximation corresponds, within integral-equation theory, to a linearized hypernetted-chain closure.

cond-mat.soft↗

arXiv2003

Colloid-Induced Polymer Compression

We consider a model mixture of hard colloidal spheres and non-adsorbing polymer chains in a theta solvent. The polymer component is modelled as a polydisperse mixture of effective spheres, mutually noninteracting but excluded from the colloids, with radii that are free to adjust to allow for colloid-induced compression. We investigate the bulk fluid demixing behaviour of this model system using a geometry-based density-functional theory that includes the polymer size polydispersity and configurational free energy, obtained from the exact radius-of-gyration distribution for an ideal (random-walk) chain. Free energies are computed by minimizing the free energy functional with respect to the polymer size distribution. With increasing colloid concentration and polymer-to-colloid size ratio, colloidal confinement is found to increasingly compress the polymers. Correspondingly, the demixing fluid binodal shifts, compared to the incompressible-polymer binodal, to higher polymer densities on the colloid-rich branch, stabilizing the mixed phase.

cond-mat.soft↗

arXiv2003

Counterion Penetration and Effective Electrostatic Interactions in Solutions of Polyelectrolyte Stars and Microgels

Counterion distributions and effective electrostatic interactions between spherical macroions in polyelectrolyte solutions are calculated via second-order perturbation (linear response) theory. By modelling the macroions as continuous charge distributions that are permeable to counterions, analytical expressions are obtained for counterion profiles and effective pair interactions in solutions of star-branched and microgel macroions. The counterions are found to penetrate stars more easily than microgels, with important implications for screening of bare macroion interactions. The effective pair interactions are Yukawa in form for separated macroions, but are softly repulsive and bounded for overlapping macroions. A one-body volume energy, which depends on the average macroion concentration, emerges naturally in the theory and contributes to the total free energy.

cond-mat.soft↗

arXiv2001

Nonlinear Screening and Effective Interactions in Charged Colloids

Influences of nonlinear screening on effective interactions between spherical macroions in charged colloids are described via response theory. Nonlinear screening, in addition to generating effective many-body interactions, is shown to entail essential corrections to the pair potential and one-body volume energy. Numerical results demonstrate that nonlinear effects can substantially modify effective interactions and thermodynamics of aqueous, low-salt suspensions of highly-charged macroions.

cond-mat.soft↗

arXiv2000

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.

cond-mat.soft↗

arXiv2000

Solid-phase structures of the Dzugutov pair potential

In recent computer simulations of a simple monatomic system interacting via the Dzugutov pair potential, freezing of the fluid into an equilibrium dodecagonal quasicrystal has been reported [M. Dzugutov, Phys. Rev. Lett. 70, 2924 (1993)]. Here, using a combination of molecular dynamics simulation and thermodynamic perturbation theory, we conduct a detailed analysis of the relative stabilities of solid-phase structures of the Dzugutov-potential system. At low pressures, the most stable structure is found to be a bcc crystal, which gives way at higher pressures to an fcc crystal. Although a dodecagonal quasicrystal and a sigma-phase crystal compete with the bcc crystal for stability, they remain always metastable.

cond-mat.stat-mech↗

arXiv1999

Effective Interactions and Volume Energies in Charge-Stabilized Colloidal Suspensions

Charge-stabilized colloidal suspensions can be conveniently described by formally reducing the macroion-microion mixture to an equivalent one-component system of pseudo-particles. Within this scheme, the utility of a linear response approximation for deriving effective interparticle interactions has been demonstrated [M. J. Grimson and M. Silbert, Mol. Phys. 74, 397 (1991)]. Here the response approach is extended to suspensions of finite-sized macroions and used to derive explicit expressions for (1) an effective electrostatic pair interaction between pseudo-macroions and (2) an associated volume energy that contributes to the total free energy. The derivation recovers precisely the form of the DLVO screened-Coulomb effective pair interaction for spherical macroions and makes manifest the important influence of the volume energy on thermodynamic properties of deionized suspensions. Excluded volume corrections are implicitly incorporated through a natural modification of the inverse screening length. By including nonlinear response of counterions to macroions, the theory may be generalized to systematically investigate effective many-body interactions.

cond-mat.soft↗

arXiv1999

Freezing of Simple Liquid Metals

Freezing of simple liquid metals and the relative stabilities of competing crystalline solids are investigated using thermodynamic perturbation theory, the interactions between ions being modeled by effective pair potentials derived from pseudopotential theory. The ionic free energy of the solid phase is calculated, to first order in the perturbation potential, using classical density-functional theory and an accurate approximation to the hard-sphere radial distribution function. Free energy calculations for Na, Mg, and Al yield well-defined freezing transitions and structural free energy differences for bcc, fcc, and hcp crystals in qualitative agreement with experiment.

cond-mat.mtrl-sci↗

arXiv1998

Stability of Colloidal Quasicrystals

Freezing of charge-stabilized colloidal suspensions and relative stabilities of crystals and quasicrystals are studied using thermodynamic perturbation theory. Macroion interactions are modelled by effective pair potentials combining electrostatic repulsion with polymer-depletion or van der Waals attraction. Comparing free energies -- counterion terms included -- for elementary crystals and rational approximants to icosahedral quasicrystals, parameters are identified for which one-component quasicrystals are stabilized by a compromise between packing entropy and cohesive energy.

cond-mat.soft↗

arXiv1997

Thermodynamically Stable One-Component Quasicrystals: A Density-Functional Survey of Relative Stabilities

A combination of classical density-functional theory and thermodynamic perturbation theory is applied to a survey of finite-temperature trends in the relative stabilities of one-component crystals and quasicrystals interacting via effective metallic pair potentials derived from pseudopotential theory. Comparing the free energies of several periodic crystals and rational approximant models of quasicrystals over a range of pseudopotential parameters, thermodynamically stable quasicrystals are predicted for parameters approaching the limits of mechanical stability of the crystal structures. Quasicrystalline stability is attributed to vibrational stiffness and energetically favorable medium- and long-range interactions. The results support and significantly extend conclusions of previous ground-state lattice-sum studies.

cond-mat.mtrl-sci↗

arXiv1997

Thermodynamically Stable One-Component Metallic Quasicrystals

Classical density-functional theory is employed to study finite-temperature trends in the relative stabilities of one-component quasicrystals interacting via effective metallic pair potentials derived from pseudopotential theory. Comparing the free energies of several periodic crystals and rational approximant models of quasicrystals over a range of pseudopotential parameters, thermodynamically stable quasicrystals are predicted for parameters approaching the limits of mechanical stability of the crystalline structures. The results support and significantly extend conclusions of previous ground-state lattice-sum studies.

cond-mat.mtrl-sci↗

arXiv1997

Density-Functional Theory of Quantum Freezing: Sensitivity to Liquid-State Structure and Statistics

Density-functional theory is applied to compute the ground-state energies of quantum hard-sphere solids. The modified weighted-density approximation is used to map both the Bose and the Fermi solid onto a corresponding uniform Bose liquid, assuming negligible exchange for the Fermi solid. The required liquid-state input data are obtained from a paired phonon analysis and the Feynman approximation, connecting the static structure factor and the linear response function. The Fermi liquid is treated by the Wu-Feenberg cluster expansion, which approximately accounts for the effects of antisymmetry. Liquid-solid transitions for both systems are obtained with no adjustment of input data. Limited quantitative agreement with simulation indicates a need for further improvement of the liquid-state input through practical alternatives to the Feynman approximation.

cond-mat.stat-mech↗

arXiv1997

Implicit Finite-Size Effects in Computer Simulations

The influence of periodic boundary conditions (implicit finite-size effects) on the anisotropy of pair correlations in computer simulations is studied for a dense classical fluid of pair-wise interacting krypton atoms near the triple point. Molecular dynamics simulation data for the pair distribution function of N-particle systems, as a function of radial distance, polar angle, and azimuthal angle are compared directly with corresponding theoretical predictions [L. R. Pratt and S. W. Haan, J. Chem. Phys. 74, 1864 (1981)]. For relatively small systems of N=60, 80, and 108 atoms, significant angular variation is observed, which is qualitatively, and in several cases quantitatively, well predicted by theory. Finite-size corrections to the spherically-averaged radial distribution function, however, are found to be comparable to random statistical errors for runs of 10^5 time steps.

cond-mat↗