arXiv subjects

A. A. Louis

Publications and source records attributed to A. A. Louis.

50 records · Page 3Linked to original sources

arXiv2001

Theory of asymmetric non-additive binary hard-sphere mixtures

We show that the formal procedure of integrating out the degrees of freedom of the small spheres in a binary hard-sphere mixture works equally well for non-additive as it does for additive mixtures. For highly asymmetric mixtures (small size ratios) the resulting effective Hamiltonian of the one-component fluid of big spheres, which consists of an infinite number of many-body interactions, should be accurately approximated by truncating after the term describing the effective pair interaction. Using a density functional treatment developed originally for additive hard-sphere mixtures we determine the zero, one, and two-body contribution to the effective Hamiltonian. We demonstrate that even small degrees of positive or negative non-additivity have significant effect on the shape of the depletion potential. The second virial coefficient $B_2$, corresponding to the effective pair interaction between two big spheres, is found to be a sensitive measure of the effects of non-additivity. The variation of $B_2$ with the density of the small spheres shows significantly different behavior for additive, slightly positive and slightly negative non-additive mixtures. We discuss the possible repercussions of these results for the phase behavior of binary hard-sphere mixtures and suggest that measurements of $B_2$ might provide a means of determining the degree of non-additivity in real colloidal mixtures.

cond-mat.soft↗

arXiv2001

Many-body interactions and correlations in coarse-grained descriptions of polymer solutions

We calculate the two, three, four, and five-body (state independent) effective potentials between the centers of mass (CM) of self avoiding walk polymers by Monte-Carlo simulations. For full overlap, these coarse-grained n-body interactions oscillate in sign as (-1)^n, and decrease in absolute magnitude with increasing n. We find semi-quantitative agreement with a scaling theory, and use this to discuss how the coarse-grained free energy converges when expanded to arbitrary order in the many-body potentials. We also derive effective {\em density dependent} 2-body potentials which exactly reproduce the pair-correlations between the CM of the self avoiding walk polymers. The density dependence of these pair potentials can be largely understood from the effects of the {\em density independent} 3-body potential. Triplet correlations between the CM of the polymers are surprisingly well, but not exactly, described by our coarse-grained effective pair potential picture. In fact, we demonstrate that a pair-potential cannot simultaneously reproduce the two and three body correlations in a system with many-body interactions. However, the deviations that do occur in our system are very small, and can be explained by the direct influence of 3-body potentials.

cond-mat.soft↗

arXiv2001

Generalized effective depletion potentials

We propose that the behavior of asymmetric binary fluid mixtures with a large class of attractive or repulsive interparticle interactions can be understood by mapping onto effective non-additive hard-sphere models. The latter are best analyzed in terms of their underlying depletion potentials which can be exactly scaled onto known additive ones. By tuning the non-additivity, a wide variety of attractive or repulsive generalized depletion potential shapes and associated phase behavior can be ``engineered'', leading, for example, to two ways to stabilize colloidal suspensions by adding smaller particles.

cond-mat.soft↗

arXiv2001

Effective potentials for polymers and colloids: Beyond the van der Waals picture of fluids?

This contribution briefly reviews some recent work demonstrating the partial breakdown of the colloidal fluid <--> atomic fluid analogy. The success of liquid state theory for atomic fluids stems in part from the van der Waals picture, where steric interactions dominate the structure, and attractive interactions can be added as a perturbation. For complex fluids described by effective potentials, this picture may break down. In the first example discussed, depletion potentials in non-additive hard-sphere mixtures are shown to be surprisingly complex, leading to fluid structure and fluid-solid transitions dominated by properties of the attractive potentials instead of by the hard-cores. Many colloidal suspensions, and possibly globular proteins, fall into this {\em energetic fluid} category. In the second example, the coarse-graining of polymers leads to soft-core effective potentials and associated {\em mean field fluid} behaviour distinguished by a breakdown of the virial expansion, an equation of state that is nevertheless nearly linear in density, and correlation functions well described by the random phase approximation.

cond-mat.soft↗

arXiv2000

Can Polymer Coils be modeled as "Soft Colloids"?

We map dilute or semi-dilute solutions of non-intersecting polymer chains onto a fluid of ``soft'' particles interacting via a concentration dependent effective pair potential, by inverting the pair distribution function of the centers of mass of the initial polymer chains. A similar inversion is used to derive an effective wall-polymer potential; these potentials are combined to successfully reproduce the calculated exact depletion interaction induced by non-intersecting polymers between two walls. The mapping opens up the possibility of large-scale simulations of polymer solutions in complex geometries.

cond-mat.soft↗

arXiv2000

Accurate effective pair potentials for polymer solutions

Dilute or semi-dilute solutions of non-intersecting self-avoiding walk (SAW) polymer chains are mapped onto a fluid of ``soft'' particles interacting via an effective pair potential between their centers of mass. This mapping is achieved by inverting the pair distribution function of the centers of mass of the original polymer chains, using integral equation techniques from the theory of simple fluids. The resulting effective pair potential is finite at all distances, has a range of the order of the radius of gyration, and turns out to be only moderately concentration-dependent. The dependence of the effective potential on polymer length is analyzed in an effort to extract the scaling limit. The effective potential is used to derive the osmotic equation of state, which is compared to simulation data for the full SAW segment model, and to the predictions of renormalization group calculations. A similar inversion procedure is used to derive an effective wall-polymer potential from the center of mass density profiles near the wall, obtained from simulations of the full polymer segment model. The resulting wall-polymer potential turns out to depend strongly on bulk polymer concentration when polymer-polymer correlations are taken into account, leading to a considerable enhancement of the effective repulsion with increasing concentration. The effective polymer-polymer and wall-polymer potentials are combined to calculate the depletion interaction induced by SAW polymers between two walls. The calculated depletion interaction agrees well with the ``exact'' results from much more computer-intensive direct simulation of the full polymer-segment model, and clearly illustrates the inadequacy -- in the semi-dilute regime -- of the standard Asakura-Oosawa approximation based on the assumption of non-interacting polymer coils.

cond-mat.soft↗

arXiv2000

Mean Field Fluid Behavior of the Gaussian Core Model

We show that the Gaussian core model of particles interacting via a penetrable repulsive Gaussian potential, first considered by Stillinger (J. Chem. Phys. 65, 3968 (1976)), behaves like a weakly correlated ``mean field fluid'' over a surprisingly wide density and temperature range. In the bulk the structure of the fluid phase is accurately described by the random phase approximation for the direct correlation function, and by the more sophisticated HNC integral equation. The resulting pressure deviates very little from a simple, mean-field like, quadratic form in the density, while the low density virial expansion turns out to have an extremely small radius of convergence. Density profiles near a hard wall are also very accurately described by the corresponding mean-field free-energy functional. The binary version of the model exhibits a spinodal instability against de-mixing at high densities. Possible implications for semi-dilute polymer solutions are discussed.

cond-mat.soft↗

arXiv2000

Fluid-solid phase-separation in hard-sphere mixtures is unrelated to bond-percolation

In a recent letter, Buhot proposes that entropy driven phase-separation in hard-core binary mixtures is directly related to a bond-percolation transition. However, at least for binary hard-sphere mixtures, calculations based on an accurate approximation to g_{ll}(r) demonstrate that n_b varies widely along the phase-boundaries calculated directly by simulations, implying that bond-percolation is unrelated to the phase-separation in these systems.

cond-mat.soft↗

arXiv1999

Crystallization and phase-separation in non-additive binary hard-sphere mixtures

We calculate for the first time the full phase-diagram of an asymmetric non-additive hard-sphere mixture. The non-additivity strongly affects the crystallization and the fluid-fluid phase-separation. The global topology of the phase-diagram is controlled by an effective size-ratio y_{eff}, while the fluid-solid coexistence scales with the depth of the effective potential well.

cond-mat.soft↗

arXiv1999

Probing Ion-Ion and Electron-Ion Correlations in Liquid Metals within the Quantum Hypernetted Chain Approximation

We use the Quantum Hypernetted Chain Approximation (QHNC) to calculate the ion-ion and electron-ion correlations for liquid metallic Li, Be, Na, Mg, Al, K, Ca, and Ga. We discuss trends in electron-ion structure factors and radial distribution functions, and also calculate the free-atom and metallic-atom form-factors, focusing on how bonding effects affect the interpretation of X-ray scattering experiments, especially experimental measurements of the ion-ion structure factor in the liquid metallic phase.

cond-mat.mtrl-sci↗

arXiv1999

Electron-Ion Structure Factors and the General Accuracy of Linear Response

We show that electron-ion structure factors in fluid metallic systems can be well understood from an application of linear response in the electron system, combined with hard-sphere like correlation for the ionic component. In particular, we predict that electron-ion structure factors fall into two general classes, one for high ($Z>3$) and one for low ($Z\leq2$) valence metals, and make suggestions for experiments to test these ideas. In addition, we show how the general success of electronic linear response for most metallic systems stems in part from an intrinsic interference between atomic and electronic length scales which weakens the nonlinear response. The main exception to this is metallic hydrogen.

cond-mat.mtrl-sci↗

arXiv1999

Extending Linear Response: Inferences from Electron-Ion Structure Factors

Linear response methods applied to electron systems often display a level of accuracy which is notable when viewed in terms of the strengths of perturbing interactions. Neglect of higher response terms is in fact justifiable in many cases and it can be shown to stem from an intrinsic interference between atomic and electronic length scales. For fluid metallic systems it can be further shown that electron-ion structure (increasingly accessible experimentally) can be understood from an application of linear response in the electron system, combined with hard-sphere like correlation for the ionic component.

cond-mat.mtrl-sci↗

arXiv1999

The structure of colloid-polymer mixtures

We investigate the structure of colloid-polymer mixtures by calculating the structure factors for the Asakura-Oosawa model in the PY approximation. We discuss the role of potential range, polymer concentration and polymer-polymer interactions on the colloid-colloid structure. Our results compare reasonably well with the recent experiments of Moussaïd et. al. for small wavenumber $k$, but we find that the Hansen-Verlet freezing criterion is violated when the liquid phase becomes marginal.

cond-mat.soft↗

arXiv1997

Metallization of Fluid Hydrogen

The electrical resistivity of liquid hydrogen has been measured at the high dynamic pressures, densities and temperatures that can be achieved with a reverberating shock wave. The resulting data are most naturally interpreted in terms of a continuous transition from a semiconducting to a metallic, largely diatomic fluid, the latter at 140 GPa, (ninefold compression) and 3000 K. While the fluid at these conditions resembles common liquid metals by the scale of its resistivity of 500 micro-ohm-cm, it differs by retaining a strong pairing character, and the precise mechanism by which a metallic state might be attained is still a matter of debate. Some evident possibilities include (i) physics of a largely one-body character, such as a band-overlap transition, (ii) physics of a strong-coupling or many-body character,such as a Mott-Hubbard transition, and (iii) processes in which structural changes are paramount.

cond-mat.mtrl-sci↗