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Richard P. Sear

Publications and source records attributed to Richard P. Sear.

51 records · Page 3Linked to original sources

Fluid-fluid transitions of hard spheres with a very short-range attraction

Hard spheres with an attraction of range a tenth to a hundredth of the sphere diameter are constrained to remain fluid even at densities when monodisperse particles at equilibrium would have crystallised, in order to compare with experimental systems which remain fluid. They are found to have a fluid-fluid transition at high density. As the range of the attraction tends to zero, the density at the critical point tends towards the random-close-packing density of hard spheres.

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Phase behaviour of a simple model of globular proteins

A simple model of globular proteins which incorporates anisotropic attractions is proposed. It is closely related to models used to model simple hydrogen-bonding molecules such as water. Theories for both the fluid and solid phases are presented, and phase diagrams calculated. The model protein exhibits a fluid-fluid transition which is metastable with respect to the fluid-solid transition for most values of the model parameters. This is behaviour often observed for globular proteins. The model offers an explanation of the difficulty observed in crystallising some globular proteins and suggests that some proteins may not have a solid phase at all under all but extreme conditions.

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Absence of the liquid phase when the attraction is not pairwise additive

Recent work on charged colloidal suspensions with very low levels of added salt has suggested that although pairs of the colloidal particles repel, clusters of the particles attract. Motivated by this, we study simple model particles which have many-body attractions. These attractions are generic many-body attractions and are not calculated for any specific colloidal suspension. We find that many-body attractions can stabilise solid phases at low pressures but that the liquid phase is either completely absent from the equilibrium phase diagram or present only within a small region of parameter space

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Classical nucleation theory for the nucleation of the solid phase of spherical particles with a short-ranged attraction

Classical nucleation theory is used to estimate the free-energy barrier to nucleation of the solid phase of particles interacting via a potential which has a short-ranged attraction. Due to the high interfacial tension between the fluid and solid phases, this barrier is very large, much larger than in hard spheres. It is divergent in the limit that the range of the attraction tends to zero. We predict an upper limit on nucleation in good agreement with the results of experiments on the crystallisation of proteins.

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The low temperature interface between the gas and solid phases of hard spheres with a short-ranged attraction

At low temperature, spheres with a very short-ranged attraction exist as a close-packed solid coexisting with an infinitely dilute gas. We find that the ratio of the interfacial tension between these two phases to the thermal energy diverges as the range of the attraction goes to zero. The large tensions when the interparticle attractions are short-ranged may be why globular proteins only crystallise over a narrow range of conditions.

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Adsorption of polydisperse polymer chains

The adsorption of polydisperse ideal polymer chains is shown to be sensitive to the large N tail of the distribution of chains. If and only if the number of chains decays more slowly than exponentially then there is an adsorption transition like that of monodisperse infinite chains. If the number decays exponentially the adsorption density diverges continuously at a temperature which is a function of the mean chain length. At low coverages, chains with repulsive monomer--monomer interactions show the same qualitative behaviour

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Depletion induced demixing in polydisperse mixtures of hard spheres

Polydisperse mixtures are those in which components with a whole range of sizes are present. It is shown that the fluid phase of polydisperse hard spheres is thermodynamically unstable unless the density of large spheres decreases at least exponentially as their size increases. The instability is with respect to the large spheres crystallising out into multiple solid phases.

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The stability limit of polydisperse sticky hard spheres

It has been shown by Stell [J. Stat. Phys. 63, 1203 (1991)] that at low temperature monodisperse sticky spheres collapse to form coexisting close-packed solid and infinitely dilute gases. We show that polydisperse sticky spheres also collapse and calculate the collapse temperature. The polydisperse spheres separate into fractions with narrower polydispersities which can then solidify. This is the first example of a single-peaked polydisperse mixture phase separating. It implies that a mixture of polydisperse large hard spheres with much smaller hard spheres does not show fluid--fluid coexistence.

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Phase separation and crystallisation of polydisperse hard spheres

Hard spheres with a polydispersity above approximately 8% are shown to crystallise into two phase-separated solid phases. A polydispersity above 8% is too large to be tolerated by a single solid phase but phase separation produces two fractions with polydispersities sufficiently narrow to allow them to crystallise. It may not be possible to observe this in experiment due to the intervention of a glass transition.

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Scattering from small colloidal particles in a semidilute polymer solution

The correlations between the segments of a semidilute polymer solution are found to induce correlations in the positions of small particles added to the solution. Small means a diameter much less than the polymer's correlation length. In the presence of polymer the particles behave as if they attracted each other. It is shown how the polymer's correlation length may be determined from a scattering experiment performed on the spheres.

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A coil-globule transition of a semiflexible polymer driven by the addition of spherical particles

The phase behaviour of a single large semiflexible polymer immersed in a suspension of spherical particles is studied. All interactions are simple excluded volume interactions and the diameter of the spherical particles is an order of magnitude larger than the diameter of the polymer. The spherical particles induce a quite long ranged depletion attraction between the segments of the polymer and this induces a continuous coil-globule transition in the polymer. This behaviour gives an indication of the condensing effect of macromolecular crowding on DNA.

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Polymer induced phase coexistence in systems of lamellar phases

The effect of adding nonadsorbing polymer to a lamellar phase of surfactant bilayers is studied theoretically. We find that the polymer produces coexistence between two lamellar phases of different layer spacings. The coexistence region is a closed loop, as in the experiments of Ficheux et al. [J. de Physique II 5 823 (1995)]. Within our model the coexistence is driven by depletion.

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Depletion driven adsorption of colloidal rods onto a hard wall

In a mixed suspension of rods and small polymer coils, the rods adsorb onto a hard wall in contact with the suspension. This adsorption is studied in the low density of rods limit. It is driven by depletion forces and is much stronger for long rods than for spheres. This is shown by means of exact, numerical, calculations and an approximate theory.

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Theory for polymer coils with necklaces of micelles

If many micelles adsorb onto the same polymer molecule then they are said to form a necklace. A minimal model of such a necklace is proposed and shown to be almost equivalent to a 1-dimensional fluid with nearest-neighbour interactions. The thermodynamic functions of this fluid are obtained and then used to predict the change in the critical micellar concentration of the surfactant in the presence of the polymer. If the amount of polymer is not too large there are two critical micellar concentrations, one for micelles in necklaces and one for free micelles.

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The coil-globule transition of polymers of long rigid monomers connected by flexible spacers

A simple model of a polymer with long rigid segments which interact via excluded volume repulsions and short ranged attractions is proposed. The coil-globule transition of this model polymer is strongly first order, the globule is crystalline and the coil which coexists with the globule is swollen. A virial expansion truncated at low order is shown to provide a very poor approximation to the free energy and so a cell theory is used to calculate the free energy of the globule.

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