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Register a new userMonolayers of hard rods on planar substrates: II. Growth
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Growth of hard--rod monolayers via deposition is studied in a lattice model using rods with discrete orientations and in a continuum model with hard spherocylinders. The lattice model is treated with kinetic Monte Carlo simulations and dynamic density functional theory while the continuum model is studied by dynamic Monte Carlo simulations equivalent to diffusive dynamics. The evolution of nematic order (excess of upright particles, standing--up transition) is an entropic effect and is mainly governed by the equilibrium solution, {rendering a continuous transition} (paper I, J. Chem. Phys. 145, 074902 (2016)). Strong non--equilibrium effects (e.g. a noticeable dependence on the ratio of rates for translational and rotational moves) are found for attractive substrate potentials favoring lying rods. Results from the lattice and the continuum models agree qualitatively if the relevant characteristic times for diffusion, relaxation of nematic order and deposition are matched properly. Applicability of these monolayer results to multilayer growth is discussed for a continuum--model realization in three dimensions where spherocylinders are deposited continuously onto a substrate via diffusion.
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The equilibrium properties of hard rod monolayers are investigated in a lattice model (where position and orientation of a rod are restricted to discrete values) as well as in an off--lattice model featuring spherocylinders with continuous positional and orientational degrees of freedom. Both models are treated using density functional theory and Monte Carlo simulations. Upon increasing the density of rods in the monolayer, there is a continuous ordering of the rods along the monolayer normal (standing up transition). The continuous transition also persists in the case of an external potential which favors flat--lying rods in the monolayer. This behavior is found in both the lattice and the continuum model. For the lattice model, we find very good agreement between the results from the specific DFT used (lattice fundamental measure theory) and simulations. The properties of lattice fundamental measure theory are further illustrated by the phase diagrams of bulk hard rods in two and three dimensions.
Based on the collision rules for hard needles we derive a hydrodynamic equation that determines the coupled translational and rotational dynamics of a tagged thin rod in an ensemble of identical rods. Specifically, based on a Pseudo-Liouville operator for binary collisions between rods, the Mori-Zwanzig projection formalism is used to derive a continued fraction representation for the correlation function of the tagged particles density, specifying its position and orientation. Truncation of the continued fraction gives rise to a generalised Enskog equation, which can be compared to the phenomenological Perrin equation for anisotropic diffusion. Only for sufficiently large density do we observe anisotropic diffusion, as indicated by an anisotropic mean square displacement, growing linearly with time. For lower densities, the Perrin equation is shown to be an insufficient hydrodynamic description for hard needles interacting via binary collisions. We compare our results to simulations and find excellent quantitative agreement for low densities and qualtitative agreement for higher densities.
Based on simplifications of previous numerical calculations [Graf and L{o}wen, Phys. Rev. E textbf{59}, 1932 (1999)], we propose algebraic free energy expressions for the smectic-A liquid crystal phase and the crystal phases of hard spherocylinders. Quantitative agreement with simulations is found for the resulting equations of state. The free energy expressions can be used to straightforwardly compute the full phase behavior for all aspect ratios and to provide a suitable benchmark for exploring how attractive interrod interactions mediate the phase stability through perturbation approaches such as free-volume or van der Waals theory.
Phase transitions are uncommon among homogenous one-dimensional fluids of classical particles owing to a general non-existence result due to van Hove. A way to circumvent van Hoves theorem is to consider an interparticle potential that is finite everywhere. Of this type is the generalized exponential model of index 4 (GEM4 potential), a model interaction which in three dimensions provides an accurate description of the effective pair repulsion between dissolved soft macromolecules (e.g., flexible dendrimers). Using specialized free-energy methods, I reconstruct the equilibrium phase diagram of the one-dimensional GEM4 system, showing that, apart from the usual fluid phase at low densities, it consists of an endless sequence of {em cluster fluid phases} of increasing pressure, having a sharp crystal appearance for low temperatures. The coexistence line between successive phases in the sequence invariably terminates at a critical point. Focussing on the first of such transitions, I show that the growth of the 2-cluster phase from the metastable ordinary fluid is extremely slow, even for large supersaturations. Finally, I clarify the apparent paradox of the observation of an activation barrier to nucleation in a system where, due to the dimensionality of the hosting space, the critical radius is expected to vanish.
We study a mass transport model, where spherical particles diffusing on a ring can stochastically exchange volume $v$, with the constraint of a fixed total volume $V=sum_{i=1}^N v_i$, $N$ being the total number of particles. The particles, referred to as $p$-spheres, have a linear size that behaves as $v_i^{1/p}$ and our model thus represents a gas of polydisperse hard rods with variable diameters $v_i^{1/p}$. We show that our model admits a factorized steady state distribution which provides the size distribution that minimizes the free energy of a polydisperse hard rod system, under the constraints of fixed $N$ and $V$. Complementary approaches (explicit construction of the steady state distribution on the one hand ; density functional theory on the other hand) completely and consistently specify the behaviour of the system. A real space condensation transition is shown to take place for $p>1$: beyond a critical density a macroscopic aggregate is formed and coexists with a critical fluid phase. Our work establishes the bridge between stochastic mass transport approaches and the optimal polydispersity of hard sphere fluids studied in previous articles.
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