Reweighting Monte Carlo Simulations Research Articles

Optimized Mie potentials for phase equilibria: Application to noble gases and their mixtures with n-alkanes.

Transferrable force fields, based on n-6 Mie potentials, are presented for noble gases. By tuning the repulsive exponent, ni, it is possible to simultaneously reproduce experimental saturated liquid densities and vapor pressures with high accuracy, from the normal boiling point to the critical point. Vapor-liquid coexistence curves for pure fluids are calculated using histogram reweighting Monte Carlo simulations in the grand canonical ensemble. For all noble gases, saturated liquid densities and vapor pressures are reproduced to within 1% and 4% of experiment, respectively. Radial distribution functions, extracted from NVT and NPT Monte Carlo simulations, are in similarly excellent agreement with experimental data. The transferability of the optimized force fields is assessed through calculations of binary mixture vapor-liquid equilibria. These mixtures include argon + krypton, krypton + xenon, methane + krypton, methane + xenon, krypton + ethane, and xenon + ethane. For all mixtures, excellent agreement with experiment is achieved without the introduction of any binary interaction parameters or multi-body interactions.

Monte Carlo predictions of phase equilibria and structure for dimethyl ether + sulfur dioxide and dimethyl ether + carbon dioxide

A new force field for dimethyl ether (DME) based on the Lennard-Jones (LJ) 12-6 plus point charge functional form is presented in this work. This force field reproduces experimental saturated liquid and vapor densities, vapor pressures, heats of vaporization, and critical properties to within the statistical uncertainty of the combined experimental and simulation measurements for temperatures between the normal boiling and critical point. Critical parameters and normal boiling point are predicted to within 0.1% of experiment. This force field is used in grand canonical histogram reweighting Monte Carlo simulations to predict the pressure composition diagrams for the binary mixtures DME + SO(2) at 363.15 K and DME + CO(2) at 335.15 and 308.15 K. For the DME + SO(2) mixture, simulation is able to qualitatively reproduce the minimum pressure azeotropy observed experimentally for this mixture, but quantitative errors exist, suggesting that multibody effects may be important in this system. For the DME + CO(2) mixture, simulation is able to predict the pressure-composition behavior within 1% of experimental data. Simulations in the isobaric-isothermal ensemble are used to determine the microstructure of DME + SO(2) and DME + CO(2) mixtures. The DME + SO(2) shows weak pairing between DME and SO(2) molecules, while no specific pairing or aggregation is observed for mixtures of DME + CO(2).

Phase behavior of a two-dimensional and confined in slitlike pores square-shoulder, square-well fluid

We report the phase diagrams for a square-shoulder, square-well fluids in two dimensions (2D), as well as confined in slitlike pores. The diagrams are obtained by histogram reweighting Monte Carlo simulations. The critical points are located by using finite size scaling analysis. Our calculations indicate that the phase behavior of the systems investigated is distinct from that observed in three dimensions. In particular, we have not found the liquid-liquid transition that occurs in the bulk.

Extension of the Transferable Potentials for Phase Equilibria Force Field to Dimethylmethyl Phosphonate, Sarin, and Soman

The transferable potentials for phase equilibria force field is extended to dimethylmethylphosphonate (DMMP), sarin, and soman by introducing a new interaction site representing the phosphorus atom. Parameters for the phosphorus atom are optimized to reproduce the liquid densities at 303 and 373 K and the normal boiling point of DMMP. Calculations for sarin and soman are performed in predictive mode, without further parameter optimization. Vapor-liquid coexistence curves, critical properties, vapor pressures and heats of vaporization are predicted over a wide range of temperatures with histogram reweighting Monte Carlo simulations in the grand canonical ensemble. Excellent agreement with experiment is achieved for all compounds, with unsigned errors of less than 1% for vapor pressures and normal boiling points and under 5% for heats of vaporization and liquid densities at ambient conditions.

Phase diagram of a square-shoulder, square-well fluid revisited

We report here the phase diagrams for a model square-shoulder, square-well fluid obtained by histogram reweighting Monte Carlo simulations. The critical points corresponding to the gas-liquid condensation and to the liquid-liquid transition have been located. Also, we have estimated the temperatures and densities at the triple points. We believe that our results are more precise and complete than those published so far.

Effect of partial charge parametrization on the fluid phase behavior of hydrogen sulfide

The effect of partial charge parametrization on the fluid phase behavior of hydrogen sulfide is investigated with grand canonical histogram reweighting Monte Carlo simulations. Four potential models, based on a Lennard-Jones + point charge functional form, are developed. It is shown that Lennard-Jones parameters can be tuned such that partial charges for the sulfur atom in the range -0.40 < q(s) < -0.252 will lead to an accurate reproduction of experimental vapor-liquid equilibria. Each of the parameter sets developed in this work are used to predict the pressure composition behavior H2S-n-pentane at 377.6 K. While the mixture calculation provides a means of reducing the number of candidate parameter sets, multiple parameter sets were found to yield an excellent reproduction of both the pure component and mixture phase behavior.

Thermodynamic properties of lattice hard-sphere models

Thermodynamic properties of several lattice hard-sphere models were obtained from grand canonical histogram- reweighting Monte Carlo simulations. Sphere centers occupy positions on a simple cubic lattice of unit spacing and exclude neighboring sites up to a distance sigma. The nearestneighbor exclusion model, sigma = radical2, was previously found to have a second-order transition. Models with integer values of sigma = 1 or 2 do not have any transitions. Models with sigma = radical3 and sigma = 3 have weak first-order fluid-solid transitions while those with sigma = 2 radical2, 2 radical3, and 3 radical2 have strong fluid-solid transitions. Pressure, chemical potential, and density are reported for all models and compared to the results for the continuum, theoretical predictions, and prior simulations when available.

The hydrophobic hydration of methane as a function of temperature from histogram reweighting Monte Carlo simulations

A microscopic explanation for the experimental observations of the solvation of methane in water is proposed by way of free energy and structural information estimated using computer simulations. In particular, the temperature dependence of both the free energy of solvation as well as structural information is calculated. The free energy is estimated by reweighting histograms from canonical and grand canonical Monte Carlo simulations along a thermodynamic path. The results for the free energy and structural changes are found to be in qualitative agreement with experimental data. We propose that the decrease in entropy found in the solvation process is brought about by excluded volume effects on mixing the two components rather than any local “freezing” of the water around the methane. At the same time the enthalpy of solvation is determined by the solute-solvent interaction. A weak dependence of the hydration free energy with temperature is found. A possible explanation lies with the relatively low temperature sensitivity of the methane–water radial distribution functions.

Phase Equilibria of Lattice Polymers from Histogram Reweighting Monte Carlo Simulations

Histogram-reweighting Monte Carlo simulations were used to obtain polymer / solvent phase diagrams for lattice homopolymers of chain lengths up to r=1000 monomers. The simulation technique was based on performing a series of grand canonical Monte Carlo calculations for a small number of state points and combining the results to obtain the phase behavior of a system over a range of temperatures and densities. Critical parameters were determined from mixed-field finite-size scaling concepts by matching the order parameter distribution near the critical point to the distribution for the three-dimensional Ising universality class. Calculations for the simple cubic lattice (coordination number z=6) and for a high coordination number version of the same lattice (z=26) were performed for chain lengths significantly longer than in previous simulation studies. The critical temperature was found to scale with chain length following the Flory-Huggins functional form. For the z=6 lattice, the extrapolated infinite chain length critical temperature is 3.70+-0.01, in excellent agreement with previous calculations of the temperature at which the osmotic second virial coefficient is zero and the mean end-to-end distance proportional to the number of bonds. This confirms that the three alternative definitions of the Theta-temperature are equivalent in the limit of long chains. The critical volume fraction scales with chain length with an exponent equal to 0.38+-0.01, in agreement with experimental data but in disagreement with polymer solution theories. The width of the coexistence curve prefactor was tentatively found to scale with chain length with an exponent of 0.20+-0.03 for z = 6 and 0.22+-0.03 for z = 26. These values are near the lower range of values obtained from experimental data.