arXiv subjects

G. Odriozola

Publications and source records attributed to G. Odriozola.

11 recordsLinked to original sources

arXiv2026

Phenol release from pNIPAM hydrogels: Scaling Molecular Dynamics simulations with Dynamical Density Functional Theory

We employed molecular dynamics simulations (MD) and Bennett's acceptance ratio method to compute the free energy of transfer (Delta G_trans) of phenol, methane, and 5-fluorouracil (5-FU) between bulk water and water-pNIPAM mixtures with different polymer volume fractions (phi_p). To this end, we first calculate the solvation free energies in both media to obtain Delta G_trans. Phenol and 5-FU (a drug used in cancer treatment) adsorb onto the pNIPAM surface and exhibit negative values of Delta G_trans irrespective of temperature, both above and below the lower critical solution temperature (T_c) of pNIPAM. In contrast, methane changes the sign of Delta G_trans, being positive below and negative above T_c. In all cases, and in contrast with some theoretical predictions, Delta G_trans shows a linear dependence on pNIPAM concentration up to high polymer densities. We also compute the diffusion coefficient (D) of phenol in water-pNIPAM mixtures as a function of phi_p in the dilute limit. Both Delta G_trans and D as functions of phi_p are key inputs to estimate the release halftime of hollow pNIPAM microgels using dynamic density functional theory (DDFT). Our scaling approach reproduces the experimental value of 2200 s for microgels of 50 micrometer radius without a cavity, at phi_p approximately 0.83 and 315 K.

cond-mat.soft↗

arXiv2015

Corresponding states law for a generalized Lennard-Jones potential

It was recently shown that vapor-liquid coexistence densities derived from Mie and Yukawa models collapse to define a single master curve when represented against the difference between the reduced second virial coefficient at the corresponding temperature and that at the critical point. In this work we further test this proposal for another generalization of the Lennard-Jones pair potential. This is carried out for vapor-liquid coexistence densities, surface tension, and vapor pressure, along a temperature window set below the critical point. For this purpose we perform molecular dynamics simulations by varying the potential softness parameter to produce from very short to intermediate attractive ranges. We observed all properties to collapse and yield master curves. Moreover, the vapor-liquid curve is found to share the exact shape of the Mie and attractive Yukawa. Furthermore, the surface tension and the logarithm of the vapor pressure are linear functions of this difference of reduced second virial coefficients.

cond-mat.stat-mech↗

arXiv2012

Hard ellipsoids: analytically approaching the exact overlap distance

Following previous work (JCP 134, 201103 (2011)), the replica exchange Monte Carlo technique is used to produce the equation of state of hard 1:5 aspect-ratio oblate ellipsoids for a wide density range. Here, in addition to the analytical approximation of the overlap distance given by Berne and Pechukas (BP) and the exact numerical solution of Perram and Wertheim, we tested a simple modification of the original BP approximation (MBP) which corrects the known T-shape mismatch of BP for all aspect-ratios. We found that the MBP equation of state shows a very good quantitative agreement with the exact solution. The MBP analytical expression allowed us to study size effects on the previously reported results. For the thermodynamic limit, we estimated the exact 1:5 hard ellipsoid isotropic-nematic transition at the volume fraction 0.343(3), and the nematic-solid transition in the volume fraction interval 0.592(6)-0.634(8).

cond-mat.stat-mech↗

arXiv2011

Equation of state of hard oblate ellipsoids by replica exchange Monte Carlo

We implemented the replica exchange Monte Carlo technique to produce the equation of state of hard 1:5 aspect-ratio oblate ellipsoids for a wide density range. For this purpose, we considered the analytical approximation of the overlap distance given by Bern and Pechukas and the exact numerical solution given by Perram and Wertheim. For both cases we capture the expected isotropic-nematic transition at low densities and a nematic-crystal transition at larger densities. For the exact case, these transitions occur at the volume fraction 0.341, and in the interval $0.584-0.605$, respectively.

cond-mat.mes-hall↗

arXiv2011

Vapor-liquid surface tension of strong short-range Yukawa fluid

The thermodynamic properties of strong short-range attractive Yukawa fluids, k=10, 9, 8, and 7, are determined by combining the slab technique with the standard and the replica exchange Monte Carlo (REMC) methods. A good agreement was found among the coexistence curves of these systems calculated by REMC and those previously reported in the literature. However, REMC allows exploring the coexistence at lower temperatures, where dynamics turns glassy. To obtain the surface tension we employed, for both methods, a procedure that yields the pressure tensor components for discontinuous potentials. The surface tension results obtained by the standard MC and REMC techniques are in good agreement.

cond-mat.soft↗

arXiv2010

Two rods confined by positive plates: Effective forces and charge distribution profiles

Monte Carlo simulations were employed to study two negative rods confined between two parallel plates. The system is immersed in a 1-1 restricted primitive model electrolyte. Ion distributions and forces per unit of area (pressures) on rods and plates are accessed by sampling the NVT ensemble. Pressures are analyzed by means of their corresponding electric and contact (depletion) contributions. This was done for several charge distributions on plates, plates charge densities, and plate-plate surface separation distances. We found an enhancement of the inherent repulsive rod-rod effective force when uncharged plates are the confining species. On the contrary, a strong decrease of the rod-rod effective repulsion was obtained for positively charged plates. Moreover, attraction was also found for plates having a charge equal to that of fully charged bilipid bilayers. These results agree with DNA-phospholipid complexation experiments. On the other hand, for a model having the plates charges fixed on a grid, very long range rod-rod sin-like effective forces were obtained. As explained in the text, they are a consequence of the rod-plate double layer coupling.

cond-mat.mes-hall↗

arXiv2010

The effect of confinement on the interaction between two like-charged rods

Monte Carlo simulations were employed to study two charged rods confined between two unlike charged plates, all immersed in a model electrolyte. Recently, it was shown that two rods immersed in a multivalent counterion solution may show attraction (PRL 78, 2477 (1997)). Here we show for a monovalent electrolyte that rod-rod attraction and repulsion can switch sign depending on confinement and ionic size. We also propose a simple self-assembling mechanism which may be helpful to understand the DNA-lipid bilayers complexation.

cond-mat.mes-hall↗

arXiv2005

Na-montmorillonite hydrates under ethane rich reservoirs: NPzzT and MuPzzT simulations

Na-montmorillonite hydrates in presence of ethane molecules are studied by means of hybrid Monte Carlo simulations in the NPzzT and MuPzzT ensembles. The NPzzT ensemble allows us to study the interlaminar distance as a function of water and ethane content. These data show clear plateaus for lower ethane contents and mainly for water contents consistent with the formation of a single water layer. In addition, from this ensemble the structure for some of these interlaminar compositions were analyzed. For systems containing few ethane molecules and water enough to complete a single layer, it was observed that ethane mainly situates close to the interlayer midplane and adopts a nearly parallel arrangement to the clay surface. On the other hand, the MuPzzT ensemble allows us to determine the interlaminar distance and water-ethane content for any specific reservoir. Here, some important findings are the following: the partial exchange of water by ethane molecules that enhances for decreasing the water vapor pressure; the obtention of a practically constant interlaminar space distance as a function of the water vapor pressure; the conservation of ion solvation shells; the enhancement of the water-ethane exchange for burial conditions; and finally, the incapability for a dehydrated clay mineral to swell in a dry and rich ethane atmosphere.

physics.chem-ph↗

arXiv2005

Stability of K-montmorillonite hydrates: Hybrid MC simulations

NPzzT and MuPzzT simulations of K-montmorillonite hydrates were performed employing hybrid Monte Carlo simulations. Two condition sets were studied, P=1 atm and T= 300 K (ground level conditions), and P=600 atm and T= 394 K; this last condition mimics a burial depth close to 4 km. For these conditions, swelling curves as a function of the reservoir water vapor pressure were built. We found the single layer K-montmorillonite hydrate stable for high vapor pressures for both, burial and ground level conditions. A simple explanation for this high stability is given.

physics.chem-ph↗

arXiv2005

Stability of Ca-montmorillonite hydrates: A computer simulation study

Classic simulations are used to study interlayer structure, swelling curves, and stability of Ca-montmorillonite hydrates. For this purpose, NPzzT$ and MuPzzT ensembles are sampled for ground level and given burial conditions. For ground level conditions, a double layer hydrate having 15.0 A of basal spacing is the predominant state for relative vapor pressures (p/po) ranging in 0.6-1.0. A triple hydrate counting on 17.9 A of interlaminar distance was also found stable for p/po=1.0. For low vapor pressures, the system may produce a less hydrated but still double layer state with 13.5 A or even a single layer hydrate with 12.2 A of interlaminar distance. This depends on the established initial conditions. On the other hand, the effect of burial conditions is two sided. It was found that it enhances dehydration for all vapor pressures except for saturation, where swelling is promoted.

physics.chem-ph↗

arXiv2002

Coupled Aggregation and Sedimentation Processes: Three Dimensional Off-Lattice Simulations

Coupled aggregation and sedimentation processes were studied by means of three dimensional computer simulations. For this purpose, a large prism with no periodic boundary conditions for the sedimentation direction was considered. Furthermore, three equally sized and mutually excluded regions were defined inside the prism, a top, a middle and a bottom region. This allows to study the time evolution of the cluster size distribution and the cluster structure separately for each region. The mass distribution profile and the center of mass position were also accessed as a function of time. For the bottom region, the effects of the sediment formation on the kinetics of growth and on the cluster structure were clearly observed. The obtained results not only agree with the experimental data obtained by Allain et. al. and with the simulations made by Gonzalez but also allow to gain further insight in the details.

cond-mat.soft↗