Theoretical and numerical study of the phase diagram of patchy colloids: ordered and disordered patch arrangements

We report theoretical and numerical evaluations of the phase diagram for a model of patchy particles. Specifically, we study hard spheres whose surface is decorated by a small number f of identical sites ("sticky spots") interacting via a short-ranged square-well attraction. We theoretically evaluate, solving the Wertheim theory, the location of the critical point and the gas-liquid coexistence line for several values of f and compare them to the results of Gibbs and grand canonical Monte Carlo simulations. We study both ordered and disordered arrangements of the sites on the hard-sphere surface and confirm that patchiness has a strong effect on the phase diagram: the gas-liquid coexistence region in the temperature-density plane is significantly reduced as f decreases. We also theoretically evaluate the locus of specific heat maxima and the percolation line.     

Energy landscape of a simple model for strong liquids

We calculate the statistical properties of the energy landscape of a minimal model for strong network-forming liquids. Dynamic and thermodynamic properties of this model can be computed with arbitrary precision even at low temperatures. A degenerate disordered ground state and logarithmic statistics for the local minima energy distribution are the landscape signatures of strong liquid behavior. Differences from fragile liquid properties are attributed to the presence of a discrete energy scale, provided by the particle bonds, and to the intrinsic degeneracy of topologically disordered networks.     

Binding of VIVO2+, VIVOL,VIVOL2 and VVO2L Moieties to Proteins: X-ray/Theoretical Characterization and Biological Implications

Vanadium compounds have frequently been proposed as therapeutics, but their application has been hampered by the lack of information on the different V-containing species that may form and how these interact with blood and cell proteins, and with enzymes. Herein, we report several resolved crystal structures of lysozyme with bound V^IVO²⁺ and V^IVOL²⁺, where L=2,2’-bipyridine or 1,10-phenanthroline (phen), and of trypsin with V^IVO(picolinato)₂ and V^VO₂(phen)⁺ moieties. Computational studies complete the refinement and shed light on the relevant role of hydrophobic interactions, hydrogen bonds, and microsolvation in stabilizating the structure. Noteworthy is that the trypsin−V^VO₂(phen) and trypsin−V^IVO(OH)(phen) adducts correspond to similar energies, thus suggesting a possible interconversion under physiological/biological conditions. The obtained data support the relevance of hydrolysis of V^IV and V^V complexes in the several types of binding established with proteins and the formation of different adducts that might contribute to their pharmacological action, and significantly widen our knowledge of vanadium–protein interactions.     

Fluid-fluid and fluid-solid transitions in the Kern-Frenkel model from Barker-Henderson thermodynamic perturbation theory

We study the Kern-Frenkel model for patchy colloids using Barker-Henderson second-order thermodynamic perturbation theory. The model describes a fluid where hard sphere particles are decorated with one patch, so that they interact via a square-well potential if they are sufficiently close one another, and if patches on each particle are properly aligned. Both the gas-liquid and fluid-solid phase coexistences are computed and contrasted against corresponding Monte Carlo simulations results. We find that the perturbation theory describes rather accurately numerical simulations all the way from a fully covered square-well potential down to the Janus limit (half coverage). In the region where numerical data are not available (from Janus to hard-spheres), the method provides estimates of the location of the critical lines that could serve as a guideline for further efficient numerical work at these low coverages. A comparison with other techniques, such as integral equation theory, highlights the important aspect of this methodology in the present context.     

Kinetic Arrest Originating in Competition Between Attractive Interaction and Packing Force

We discuss the situation where attractive and repulsive portions of the interparticle potential both contribute significantly to glass formation. We introduce the square-well potential as prototypical model for this situation, and reject the Baxter model as a useful model for comparison to experiment on glasses, based on our treatment within mode coupling theory. We present explicit results for various well widths, and show that, for narrow wells, there is a useful analytical formula that would be suitable for experimentalists working in the field of colloidal science. We raise the question as to whether, in a more exact treatment, the sticky-sphere limit might have an infinite glass transition temperature or a high but finite one.     

A phenomenological approach to relaxation in disordered systems

We propose a phenomenological approach to relaxation in disordered systems which is modelled after the well-known percolation behaviour. The approach shows an interesting behaviour of the time correlation function of relevant variables which is characterized by three temporal regimes, an initial exponential decay, a power-law regime and a stretched exponential decay for long times. We give some relevant examples of this behaviour in a wide variety of systems such as gels, microemulsions and glasses.     

Study of the ST2 model of water close to the liquid-liquid critical point

We perform successive umbrella sampling grand canonical Monte Carlo computer simulations of the original ST2 model of water in the vicinity of the proposed liquid-liquid critical point, at temperatures above and below the critical temperature. Our results support the previous work of Y. Liu, A. Z. Panagiotopoulos and P. G. Debenedetti [J. Chem. Phys., 2009, 131, 104508], who provided evidence for the existence and location of the critical point for ST2 using the Ewald method to evaluate the long-range forces. Our results therefore demonstrate the robustness of the evidence for critical behavior with respect to the treatment of the electrostatic interactions. In addition, we verify that the liquid is equilibrated at all densities on the Monte Carlo time scale of our simulations, and also that there is no indication of crystal formation during our runs. These findings demonstrate that the processes of liquid-state relaxation and crystal nucleation are well separated in time. Therefore, the bimodal shape of the density of states, and hence the critical point itself, is a purely liquid-state phenomenon that is distinct from the crystal-liquid transition.     

From caging to Rouse dynamics in polymer melts with intramolecular barriers: a critical test of the mode coupling theory

By means of computer simulations and solution of the equations of the mode coupling theory (MCT), we investigate the role of the intramolecular barriers on several dynamic aspects of nonentangled polymers. The investigated dynamic range extends from the caging regime characteristic of glass-formers to the relaxation of the chain Rouse modes. We review our recent work on this question, provide new results, and critically discuss the limitations of the theory. Solutions of the MCT for the structural relaxation reproduce qualitative trends of simulations for weak and moderate barriers. However, a progressive discrepancy is revealed as the limit of stiff chains is approached. This disagreement does not seem related with dynamic heterogeneities, which indeed are not enhanced by increasing barrier strength. It is not connected either with the breakdown of the convolution approximation for three-point static correlations, which retains its validity for stiff chains. These findings suggest the need of an improvement of the MCT equations for polymer melts. Concerning the relaxation of the chain degrees of freedom, MCT provides a microscopic basis for time scales from chain reorientation down to the caging regime. It rationalizes, from first principles, the observed deviations from the Rouse model on increasing the barrier strength. These include anomalous scaling of relaxation times, long-time plateaux, and nonmonotonous wavelength dependence of the mode correlators.