Capillary condensation between nonparallel walls.

We study the condensation of fluids confined by a pair of nonparallel plates of finite height H. We show that such a system experiences two types of condensation, termed single and double pinning, which can be characterized by one (single-pinning) or two (double-pinning) edge contact angles describing the shape of menisci pinned at the system edges. For both types of capillary condensation, we formulate the Kelvin-like equation and determine the conditions under which the given type of condensation occurs. We construct the global phase diagram revealing a reentrant phenomenon pertinent to the change of the capillary condensation type upon varying the inclination of the walls. Asymptotic properties of the system are discussed and a link with related phase phenomena in different systems is made. Finally, we show that the change from a single- to a double-pinned state is a continuous transition, the character of which depends on the wetting properties of the walls.

Novel barostat implementation for molecular dynamics.

We propose a novel implementation of the extended-dynamics equations for isothermal-isobaric ensemble in molecular dynamics, as the Martyna-Tobias-Klein thermostat and barostat. This method is suitable for systems with constraints and the Verlet-family integrators. Instead of iterations or the Trotter-expansion-based methods, both velocities and box sizes (scaling of bond lengths) are predicted. The algorithm begins with force calculation, requiring neither quarter nor half time steps, and necessitating iterations only inside SHAKE. Several tests demonstrate that the quality is comparable to other implementations. It is found that the formula relating the extended barostat mass to the characteristic time of volume fluctuations is inaccurate for condensed systems, which has consequences for the parameter setup. Emphasis is also put on the verification of the precise isothermal-isobaric ensemble and finite-size effects.

Properties of water and argon clusters developed in supersonic expansions.

Using adiabatic molecular dynamics coupled with the fluid dynamics equations, we model nucleation in an expanding beam of water vapor and argon on a microsecond scale. The size distribution of clusters, their temperature, and pickup cross sections in dependence on velocity are investigated and compared to the geometric cross sections and the experiment. The clusters are warmer than the expanding gas because of the time scale of relaxation processes. We also suggest that their translational and rotational kinetic energies are modified due to evaporative cooling. The pickup cross sections determined for the final clusters using molecules of the same kind increase with decreasing velocity, still obeying the (a+bN1/3)2 law.