RESUMEN

The Ewald method has been the cornerstone in molecular simulations for modeling electrostatic interactions of charge-stabilized many-body systems. In the late 1990s, Wolf and collaborators developed an alternative route to describe the long-range nature of electrostatic interactions; from a computational perspective, this method provides a more efficient and straightforward way to implement long-range electrostatic interactions than the Ewald method. Despite these advantages, the validity of the Wolf potential to account for the electrostatic contribution in charged fluids remains controversial. To alleviate this situation, in this contribution, we implement the Wolf summation method to both electrolyte solutions and charged colloids with moderate size and charge asymmetries in order to assess the accuracy and validity of the method. To this end, we verify that the proper selection of parameters within the Wolf method leads to results that are in good agreement with those obtained through the standard Ewald method and the theory of integral equations of simple liquids within the so-called hypernetted chain approximation. Furthermore, we show that the results obtained with the original Wolf method do satisfy the moment conditions described by the Stillinger-Lovett sum rules, which are directly related to the local electroneutrality condition and the electrostatic screening in the Debye-Hückel regime. Hence, the fact that the solution provided by the Wolf method satisfies the first and second moments of Stillinger-Lovett proves, for the first time, the reliability of the method to correctly incorporate the electrostatic contribution in charge-stabilized fluids. This makes the Wolf method a powerful alternative compared to more demanding computational approaches.

RESUMEN

We report results of a molecular dynamics simulation study of the effect of one general anesthetic, halothane, on some properties of mixed DPPC/DPPE phospholipid membranes. This is a suitable model for the study of simple, two-phospholipid membrane systems. From the simulation runs, we determined several membrane properties for five different molecular proportions of DPPC/DPPE. The effect of halothane on the studied membrane properties (area per lipid molecule, density of membrane, order parameter, etc.) was rather small. The distribution of halothane is not uniform through the bilayer thickness. Instead, there is a maximum of anesthetic concentration around 1.2 nm from the center of the membrane. The anesthetic molecule is located close to the phospholipid headgroups. The position of the halothane density maximum depends slightly on the DPPC/DPPE molar proportion. Snapshots taken over the plane of the membrane, as well as calculated two-dimensional radial distribution functions show that the anesthetic has no preference for either phospholipid (DPPC or DPPE). Our results indicate that this anesthetic molecule has only small effects on DPPC/DPPE mixed membranes. In addition, halothane displays no preferential location around DPPC or DPPE. This is probably due to the hydrophobic nature of halothane and to the fact that the chosen phospholipids have the same hydrophobic tails.

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RESUMEN

The topological analysis tool known as the common neighbor analysis (CNA) is used for the first time in this work to analyze crystallization kinetics and excess entropy of charge-stabilized colloidal suspensions. For this purpose, Brownian dynamics computer simulations are implemented to investigate the crystallization kinetics of homogeneously melted colloidal crystals that are composed of hard-core-screened-Coulomb interacting particles. The results are in agreement with recent static structure factor measurements that could indicate the presence of icosahedral units in the metastable melt, and with the fact that weakly screened charged colloids crystallize into body-centered-cubic (bcc) ordering. A two-step crystallization pathway is found, in which the population of bcc-subunit CNA-pairs satisfactorily obeys a Verhulst model. Moreover, the CNA helped to unveil that the excess entropy obeys a quasi-universal functional form, relating the behavior of colloidal, molecular, and metallic liquid systems. The work contributes to the scientific understanding of the crystallization pathway of charged colloids, and to the development of new ways to assess the degree of crystalline order, starting from the excess entropy.

RESUMEN

The long-time self-diffusion coefficient, D(L), of charged spherical colloidal particles in parallel planar layers is studied by means of Brownian dynamics computer simulations and mode-coupling theory. All particles (regardless which layer they are located on) interact with each other via the screened Coulomb potential and there is no particle transfer between layers. As a result of the geometrical constraint on particle positions, the simulation results show that D(L) is strongly controlled by the separation between layers. On the basis of the so-called contraction of the description formalism [C. Contreras-Aburto, J. M. Méndez-Alcaraz, and R. Castañeda-Priego, J. Chem. Phys. 132, 174111 (2010)], the effective potential between particles in a layer (the so-called observed layer) is obtained from integrating out the degrees of freedom of particles in the remaining layers. We have shown in a previous work that the effective potential performs well in describing the static structure of the observed layer (loc. cit.). In this work, we find that the D(L) values determined from the simulations of the observed layer, where the particles interact via the effective potential, do not agree with the exact values of D(L). Our findings confirm that even when an effective potential can perform well in describing the static properties, there is no guarantee that it will correctly describe the dynamic properties of colloidal systems.