Understanding the growth of organic semi-conducting molecules with shape anisotropy is of high relevance to the processing of optoelectronic devices. This work provides insight into the growth of thin films of the prototypical rodlike organic semicon
ductor diindenoperylene on a microscopic level, by analyzing in detail the film morphology. We model our data, which were obtained by high-resolution grazing incidence small angle x-ray scattering (GISAXS), using a theoretical description from small angle scattering theory derived for simple liquids. Based on form factor calculations for different object types we determine how the island shapes change in the respective layers. Atomic force microscopy measurements approve our findings.
We investigate the evolution of a system of colloidal particles, trapped at a fluid interface and interacting via capillary attraction, as function of the range of the capillary interaction and temperature. We address the collapse of an initially hom
ogeneous particle distribution and of a radially symmetric (disk--shaped) distribution of finite size, both theoretically by using a perturbative approach inspired by cosmological models and numerically by means of Brownian dynamics (BD) and dynamical density functional theory (DDFT). The results are summarized in a dynamical phase diagram, describing a smooth crossover from collective (gravitational-like) collapse to local (spinodal-like) clustering. In this crossover region, the evolution exhibits a peculiar shock wave behavior at the outer rim of the contracting, disk-shaped distribution.
In materials science the phase field crystal approach has become popular to model crystallization processes. Phase field crystal models are in essence Landau-Ginzburg-type models, which should be derivable from the underlying microscopic description
of the system in question. We present a study on classical density functional theory in three stages of approximation leading to a specific phase field crystal model, and we discuss the limits of applicability of the models that result from these approximations. As a test system we have chosen the three--dimensional suspension of monodisperse hard spheres. The levels of density functional theory that we discuss are fundamental measure theory, a second-order Taylor expansion thereof, and a minimal phase-field crystal model. We have computed coexistence densities, vacancy concentrations in the crystalline phase, interfacial tensions and interfacial order parameter profiles, and we compare these quantities to simulation results. We also suggest a procedure to fit the free parameters of the phase field crystal model.
We perform a comparative study of the free energies and the density distributions in hard sphere crystals using Monte Carlo simulations and density functional theory (employing Fundamental Measure functionals). Using a recently introduced technique (
Schilling and Schmid, J. Chem. Phys 131, 231102 (2009)) we obtain crystal free energies to a high precision. The free energies from Fundamental Measure theory are in good agreement with the simulation results and demonstrate the applicability of these functionals to the treatment of other problems involving crystallization. The agreement between FMT and simulations on the level of the free energies is also reflected in the density distributions around single lattice sites. Overall, the peak widths and anisotropy signs for different lattice directions agree, however, it is found that Fundamental Measure theory gives slightly narrower peaks with more anisotropy than seen in the simulations. Among the three types of Fundamental Measure functionals studied, only the White Bear II functional (Hansen-Goos and Roth, J. Phys.: Condens. Matter 18, 8413 (2006)) exhibits sensible results for the equilibrium vacancy concentration and a physical behavior of the chemical potential in crystals constrained by a fixed vacancy concentration.
We study the excess free energy due to phase coexistence of fluids by Monte Carlo simulations using successive umbrella sampling in finite LxLxL boxes with periodic boundary conditions. Both the vapor-liquid phase coexistence of a simple Lennard-Jone
s fluid and the coexistence between A-rich and B-rich phases of a symmetric binary (AB) Lennard-Jones mixture are studied, varying the density rho in the simple fluid or the relative concentration x_A of A in the binary mixture, respectively. The character of phase coexistence changes from a spherical droplet (or bubble) of the minority phase (near the coexistence curve) to a cylindrical droplet (or bubble) and finally (in the center of the miscibility gap) to a slab-like configuration of two parallel flat interfaces. Extending the analysis of M. Schrader, P. Virnau, and K. Binder [Phys. Rev. E 79, 061104 (2009)], we extract the surface free energy gamma (R) of both spherical and cylindrical droplets and bubbles in the vapor-liquid case, and present evidence that for R -> Infinity the leading order (Tolman) correction for droplets has sign opposite to the case of bubbles, consistent with the Tolman length being independent on the sign of curvature. For the symmetric binary mixture the expected non-existence of the Tolman length is confirmed. In all cases {and for a range of radii} R relevant for nucleation theory, gamma(R) deviates strongly from gamma (Infinity) which can be accounted for by a term of order gamma(Infinity)/gamma(R)-1 ~ 1/R^2. Our results for the simple Lennard-Jones fluid are also compared to results from density functional theory and we find qualitative agreement in the behavior of gamma(R) as well as in the sign and magnitude of the Tolman length.
We report on a large scale computer simulation study of crystal nucleation in hard spheres. Through a combined analysis of real and reciprocal space data, a picture of a two-step crystallization process is supported: First dense, amorphous clusters f
orm which then act as precursors for the nucleation of well-ordered crystallites. This kind of crystallization process has been previously observed in systems that interact via potentials that have an attractive as well as a repulsive part, most prominently in protein solutions. In this context the effect has been attributed to the presence of metastable fluid-fluid demixing. Our simulations, however, show that a purely repulsive system (that has no metastable fluid-fluid coexistence) crystallizes via the same mechanism.
