arXiv subjects

Martin Horsch

Publications and source records attributed to Martin Horsch.

26 records · Page 2Linked to original sources

arXiv2010

Molecular modeling of hydrogen bonding fluids: Vapor-liquid coexistence and interfacial properties

A major challenge for molecular modeling consists in optimizing the unlike interaction potentials. In many cases, combination rules are generally suboptimal when accurate predictions of properties like the mixture vapor pressure are needed. However, the well known Lorentz-Berthelot rule performs quite well and can be used as a starting point. If more accurate results are required, it is advisable to adjust the dispersive interaction energy parameter. In the present study, mixture properties are explored for binary systems containing hydrogen bonding components. Furthermore, vapor-liquid interface cluster criteria and contact angles are discussed and remarks on computational details are given. Finally, a sterically accurate generic model for benzyl alcohol is introduced and evaluated.

physics.comp-ph↗

arXiv2010

The air pressure effect on the homogeneous nucleation of carbon dioxide by molecular simulation

Vapour-liquid equilibria (VLE) and the influence of an inert carrier gas on homogeneous vapour to liquid nucleation are investigated by molecular simulation for quaternary mixtures of carbon dioxide, nitrogen, oxygen, and argon. Canonical ensemble molecular dynamics simulation using the Yasuoka-Matsumoto method is applied to nucleation in supersaturated vapours that contain more carbon dioxide than in the saturated state at the dew line. Established molecular models are employed that are known to accurately reproduce the VLE of the pure fluids as well as their binary and ternary mixtures. On the basis of these models, also the quaternary VLE properties of the bulk fluid are determined with the Grand Equilibrium method. Simulation results for the carrier gas influence on the nucleation rate are compared with the classical nucleation theory (CNT) considering the "pressure effect" [Phys. Rev. Lett. 101: 125703 (2008)]. It is found that the presence of air as a carrier gas decreases the nucleation rate only slightly and, in particular, to a significantly lower extent than predicted by CNT. The nucleation rate of carbon dioxide is generally underestimated by CNT, leading to a deviation between one and two orders of magnitude for pure carbon dioxide in the vicinity of the spinodal line and up to three orders of magnitude in presence of air as a carrier gas. Furthermore, CNT predicts a temperature dependence of the nucleation rate in the spinodal limit, which cannot be confirmed by molecular simulation.

physics.ao-ph↗

arXiv2009

Poiseuille flow of liquid methane in nanoscopic graphite channels by molecular dynamics simulation

MD simulations of methane confined between graphite walls with up to 4,800,000 interaction sites, i.e., carbon atoms and methane molecules, are conducted, where the channel width is varied to include both the boundary-dominated regime and the transition to the continuum regime. This proves that MD can be used today to cover the entire range of characteristic lengths for which continuum methods fail.

cond-mat.mes-hall↗

arXiv2009

Steady-state molecular dynamics simulation of vapour to liquid nucleation with McDonald's daemon

The most interesting step of condensation is the cluster formation up to the critical size. In a closed system, this is an instationary process, as the vapour is depleted by the emerging liquid phase. This imposes a limitation on direct molecular dynamics (MD) simulation of nucleation by affecting the properties of the vapour to a significant extent so that the nucleation rate varies over simulation time. Grand canonical MD with McDonald's daemon is discussed in the present contribution and applied for sampling both nucleation kinetics and steady-state properties of a supersaturated vapour. The idea behind that approach is to simulate the production of clusters up to a given size for a specified supersaturation. In that way, nucleation is studied by a steady-state simulation. A series of simulations is conducted for the truncated and shifted Lennard-Jones fluid which accurately describes the fluid phase coexistence of noble gases and methane. The classical nucleation theory is found to overestimate the free energy of cluster formation and to deviate by two orders of magnitude from the nucleation rate below the triple point at high supersaturations.

physics.ao-ph↗

arXiv2009

Grand canonical steady-state simulation of nucleation

Grand canonical molecular dynamics (GCMD) is applied to the nucleation process in a metastable phase near the spinodal, where nucleation occurs almost instantaneously and is limited to a very short time interval. With a variant of Maxwell's demon, proposed by McDonald [Am. J. Phys. 31: 31 (1963)], all nuclei exceeding a specified size are removed. In such a steady-state simulation, the nucleation process is sampled over an arbitrary timespan and all properties of the metastable state, including the nucleation rate, can be obtained with an increased precision. As an example, a series of GCMD simulations with McDonald's demon is carried out for homogeneous vapor to liquid nucleation of the truncated-shifted Lennard-Jones (tsLJ) fluid, covering the entire relevant temperature range. The results are in agreement with direct non-equilibrium MD simulation in the canonical ensemble. It is confirmed for supersaturated vapors of the tsLJ fluid that the classical nucleation theory underpredicts the nucleation rate by two orders of magnitude.

physics.comp-ph↗

arXiv2009

Molecular modeling and simulation of thermophysical properties: Application to pure substances and mixtures

At the Institute for Thermodynamics and Thermal Process Engineering (ITT) about 100 molecular models for pure substances have been developed so far. These models reproduce vapor pressure, saturated liquid density, and enthalpy of vaporization with a technical accuracy of less than 5%, less than 1%, and less than 5% deviation compared to experimental data, respectively. Simulation results are outlined for the pure substances ethylene oxide and ammonia, demonstrating the outstanding predictive power of the applied methods. Secondly, nucleation processes are discussed. Underlying effects on are studied on the molecular level.

physics.comp-ph↗

arXiv2009

Homogeneous nucleation in supersaturated vapors of methane, ethane, and carbon dioxide predicted by brute force molecular dynamics

Molecular dynamics (MD) simulation is applied to the condensation process of supersaturated vapors of methane, ethane, and carbon dioxide. Simulations of systems with up to a million particles were conducted with a massively parallel MD program. This leads to reliable statistics and makes nucleation rates down to the order of 10^30/(m^3 s) accessible to the direct simulation approach. Simulation results are compared to the classical nucleation theory (CNT) as well as the theory of Laaksonen, Ford, and Kulmala (LFK) which introduces a size dependence of the specific surface energy. CNT describes the nucleation of ethane and carbon dioxide excellently over the entire studied temperature range, whereas LFK provides a better approach to methane at low temperatures.

physics.chem-ph↗

arXiv2009

Modification of the classical nucleation theory based on molecular simulation data for surface tension, critical nucleus size, and nucleation rate

Nucleation in supersaturated vapor is investigated with two series of molecular dynamics simulations in the canonical ensemble. The applied methods are: (a) analysis of critical nuclei at moderate supersaturations by simulating equilibria of single droplets with surrounding vapors in small systems; (b) simulation of homogeneous nucleation during condensation with large systems containing 10^5 to 10^6 particles for calculating the nucleation rate of vapors at high supersaturations. For the Lennard-Jones fluid, truncated and shifted at 2.5 times the size parameter, it is shown that the classical nucleation theory underestimates both the nucleation rate and the size of the critical nucleus. A surface property corrected modification of this theory is proposed to consistently cover data on the surface tension of the curved interface, the critical nucleus size, and the nucleation rate.

physics.chem-ph↗