Biomedical subjects

Philippe Ungerer

Publications and source records attributed to Philippe Ungerer.

6 recordsLinked to original sources

PubMed2006

Molecular simulation studies of water physisorption in zeolites.

We report a series of Grand Canonical Monte Carlo simulations of water adsorption in NaY and NaX faujasite, as well as in silicalite-1. Computed adsorption isotherms and heats of adsorption were in good agreement with the available experiments. The existence of cyclic water hexamers in NaX located in the 12-ring windows, recently disclosed by neutron diffraction experiments (Hunger et al., J. Phys. Chem. B, 2006, 110, 342-353) was reproduced in our simulations. Interestingly enough, such cyclic hexamer clusters were also observed in the case of NaY, in which no stabilizing cation is present in the 12-ring window. We also report cation redistribution upon water adsorption for sodium faujasite with varying cation contents (Si ratio Al ratio in the range 1.53-3). A simple and transferable forcefield was used, that enabled to reproduce the different aspects of water physisorption in stable zeolites. The high pressure water condensation in hydrophobic silicalite-1 was reproduced without any parameter readjustment. The method and forcefield used here should be useful for engineering oriented applications such as the prediction of multi-component mixture adsorptive separations in various stable zeolites. It allows to address the issue of the effect of the small amounts of water that are almost inevitably present in zeolite-based separation processes.

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PubMed2006

Critical point estimation of the Lennard-Jones pure fluid and binary mixtures.

The apparent critical point of the pure fluid and binary mixtures interacting with the Lennard-Jones potential has been calculated using Monte Carlo histogram reweighting techniques combined with either a fourth order cumulant calculation (Binder parameter) or a mixed-field study. By extrapolating these finite system size results through a finite size scaling analysis we estimate the infinite system size critical point. Excellent agreement is found between all methodologies as well as previous works, both for the pure fluid and the binary mixture studied. The combination of the proposed cumulant method with the use of finite size scaling is found to present advantages with respect to the mixed-field analysis since no matching to the Ising universal distribution is required while maintaining the same statistical efficiency. In addition, the accurate estimation of the finite critical point becomes straightforward while the scaling of density and composition is also possible and allows for the estimation of the line of critical points for a Lennard-Jones mixture.

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PubMed2006

Optimization of the anisotropic united atoms intermolecular potential for n-alkanes: improvement of transport properties.

The parameters of the anisotropic united atom (AUA) intermolecular potential for n-alkanes originally proposed by Toxvaerd [J. Chem. Phys. 93, 4290 (1990)] [AUA(3)] was optimized by Ungerer et al. [J. Chem. Phys. 112, 5499 (2000)] [AUA(4)] on the basis of equilibrium properties (vapor pressures, vaporization enthalpies, and liquid densities). In this work we analyze the influence of the torsion potential in the internal and collective dynamics of the AUA model. The modified potential [AUA(4m)] preserves all the intermolecular parameters and only explores an increment in the trans-gauche and gauche(+)-gauche(-) transition barrier of the torsion potential. This modification better reproduce different transport properties (shear viscosity, self-diffusion coefficient, and internal relaxation times), keeping the accuracy achieved in our previous work for equilibrium properties. An extensive investigation of the shear viscosity of ethane, n-pentane, n-dodecane, and n-eicosane in a wide range of pressures and temperatures shows that the AUA(4m) improves the accuracy of the original AUA(4), reducing the absolute average deviation from 30% to 14.5%. Finally, the self-diffusion coefficient of n-hexane computed with the new model in the range of 223-333 K and from 0.1 to 295 MPa is in better agreement with respect to the experimental data than the original model.

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PubMed2006

Low-temperature vapor-liquid equilibria from parallelized molecular dynamics simulations. Application to 1- and 2-methylnaphthalene.

A parallelized sampling version of the Gibbs Ensemble (Mol. Phys. 2000, 98, 1887) has been implemented to predict low-temperature vapor-liquid equilibria of 1- and 2-methylnaphthalene modeled by anisotropic united atom potentials. The simulation were performed at the low temperature of 364.2 K at which common direct simulation methods fail due to particle transfer problems. The simulation results are compared with published results obtained from the Gibbs-Duhem integration method and with experimental data. Both methods are compared and discussed in terms of computational efficiency and with respect to their future use at other thermodynamic conditions.

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PubMed2005

Optimized intermolecular potential for aromatic hydrocarbons based on anisotropic united atoms. III. Polyaromatic and naphthenoaromatic hydrocarbons.

In this third article of the series, a new anisotropic united atoms (AUA) intermolecular potential parameter set has been proposed for the carbon force centers connecting the aromatic rings of polyaromatic hydrocarbons to predict thermodynamic properties using both the Gibbs ensemble and NPT Monte Carlo simulations. The model uses the same parameters as previous AUA models used for the aromatic CH force centers. The optimization procedure is based on the minimization of a dimensionless error criterion incorporating various thermodynamic data of naphthalene at 400 and 550 K. The new model has been evaluated on a series of polyaromatic and naphthenoaromatic hydrocarbons over a wide range of temperatures up to near-critical conditions. Vaporization enthalpy, liquid density, and normal boiling temperature are reproduced with good accuracy. The new potential parameters have also been tested successfully on toluene, 1,3,5-trimethylbenzene, styrene, m-xylene, n-hexylbenzene, and n-dodecylbenzene to demonstrate their transferability to alkylbenzenes.

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PubMed2004

Dynamical and structural properties of benzene in supercritical water.

We have employed an anisotropic united atom model of benzene (R. O. Contreras, Ph.D. thesis, Universitat Rovira i Virgili 2002) that reproduces the quadrupolar moment of this molecule through the inclusion of seven point charges. We show that this kind of interaction is required to reproduce the solvation of these molecules in supercritical water. We have computed self-diffusion coefficient and Maxwell-Stefan coefficients as well as the shear viscosity for the mixture water-benzene at supercritical conditions. A strong density and composition dependence of these properties is observed. In addition, our simulations are in qualitative agreement with the experimental evidence that, at medium densities (0.6 g/cm(3) and 673 K), almost half of the benzene molecules have one hydrogen bond with water molecules. We also observe that these bonds are longer lived than the corresponding hydrogen bonds between water molecules. Similarly, we obtain an important reduction of the dielectric constant of the mixture with the increment of the amount of benzene molecules at medium and high densities.

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