Search results for " canonical"

Wetting of polymer liquids: Monte Carlo simulations and self-consistent field calculations

2003

Using Monte Carlo simulations and self-consistent field (SCF) theory we study the surface and interface properties of a coarse grained off-lattice model. In the simulations we employ the grand canonical ensemble together with a reweighting scheme in order to measure surface and interface free energies and discuss various methods for accurately locating the wetting transition. In the SCF theory, we use a partial enumeration scheme to incorporate single-chain properties on all length scales and use a weighted density functional for the excess free energy. The results of various forms of the density functional are compared quantitatively to the simulation results. For the theory to be accurate…

Surface Charge Density and Electrokinetic Potential of Highly Charged Minerals: Experiments and Monte Carlo Simulations on Calcium Silicate Hydrate

2006

International audience; In this paper, we are concerned with the charging and electrokinetic behavior of colloidal particles exhibiting a high surface charge in the alkaline pH range. For such particles, a theoretical approach has been developed in the framework of the primitive model. The charging and electrokinetic behavior of the particles are determined by the use of a Monte Carlo simulation in a grand canonical ensemble and compared with those obtained through the mean field theory. One of the most common colloidal particles has been chosen to test our theoretical approach. That is calcium silicate hydrate (C−S−H) which is the main component of hydrated cement and is known for being re…

Equation of State for Macromolecules of Variable Flexibility in Good Solvents: A Comparison of Techniques for Monte Carlo Simulations of Lattice Mode…

2007

The osmotic equation of state for the athermal bond fluctuation model on the simple cubic lattice is obtained from extensive Monte Carlo simulations. For short macromolecules (chain length N=20) we study the influence of various choices for the chain stiffness on the equation of state. Three techniques are applied and compared in order to critically assess their efficiency and accuracy: the repulsive wall method, the thermodynamic integration method (which rests on the feasibility of simulations in the grand canonical ensemble), and the recently advocated sedimentation equilibrium method, which records the density profile in an external (e.g. gravitation-like) field and infers, via a local …

Thermal density fluctuations in amorphous polymers as revealed by small angle X-ray diffraction

1973

In the case of equilibrium the mean square relative fluctuations of the thermodynamic parameters vanish asymptotically as the number of degrees of freedom approach infinity. There are various observable effects, however, which are related to local fluctuations of the thermodynamic quantities within small parts of the macroscopic system. In particular the scattering of electromagnetic waves by a one-component, one-phase system is due to thermal density fluctuations within small volumes V of the sample. Considering a grand canonical ensemble the phenomenological theory of local fluctuations (1) for a one component system shows that the fluctuation of the number of particles N in the volume V …

Electrocatalytic thermodynamics and kinetics at constant electrode potentials: The grand canonical ensemble approach

2020

Determination of the origin and magnitude of logarithmic finite-size effects on interfacial tension: Role of interfacial fluctuations and domain brea…

2014

The ensemble-switch method for computing wall excess free energies of condensed matter is extended to estimate the interface free energies between coexisting phases very accurately. By this method, system geometries with linear dimensions $L$ parallel and $L_z$ perpendicular to the interface with various boundary conditions in the canonical or grandcanonical ensemble can be studied. Using two- and three-dimensional Ising models, the nature of the occurring logarithmic finite size corrections is studied. It is found crucial to include interfacial fluctuations due to "domain breathing".

Suspensions of rod-like colloids and a depleting agent under confinement

2008

We present a computer simulation study of suspensions of rod-like colloids and a depletant in confinement to a slit-pore. Mixtures of hard spherocylinders and ideal spheres were studied by means of Monte Carlo simulations in the grand canonical ensemble. By use of finite size scaling analysis we determined the critical behaviour. In order to overcome large barriers in the free energy we applied the successive umbrella sampling method (Virnau and Muller 2004 J. Chem. Phys. 120 10925). We find that, under confinement, the critical point of gas–liquid demixing shifts to higher concentrations of rods and smaller concentrations of spheres due to the formation of an orientationally ordered surfac…

Metastability of Traffic Flow in Zero-Range Model

2007

The development of traffic jams in vehicular flow is an everyday example of the occurence of phase separation in low-dimensional driven systems, a topic which has attracted much recent interest [1–4]. In [5] the existence of phase separation is related to the size-dependence of domain currents and a quantitative criterion is obtained by considering the zero-range process (ZRP) as a generic model for domain dynamics. We use zero-range picture to study the phase separation in traffic flow in the spirit of the probabilistic (master equation) description of transportation [6]. Significantly, we find [7] that prior to condensation studied in previous works [8, 9] the system can exist in a homoge…

Grand canonical ensemble approach to electrochemical thermodynamics, kinetics, and model Hamiltonians

2021

The unique feature of electrochemistry is the ability to control reaction thermodynamics and kinetics by the application of electrode potential. Recently, theoretical methods and computational approaches within the grand canonical ensemble (GCE) have enabled to explicitly include and control the electrode potential in first principles calculations. In this review, recent advances and future promises of GCE density functional theory and rate theory are discussed. Particular focus is devoted to considering how the GCE methods either by themselves or combined with model Hamiltonians can be used to address intricate phenomena such as solvent/electrolyte effects and nuclear quantum effects to pr…

Might exogenous circular RNAs act as protein-coding transcripts in plants?

2021

Circular RNAs (circRNAs) are regulatory molecules involved in the modulation of gene expression. Although originally assumed as non-coding RNAs, recent studies have evidenced that animal circRNAs can act as translatable transcripts. The study of plant-circRNAs is incipient, and no autonomous coding plant-circRNA has been described yet. Viroids are the smallest plant-pathogenic circRNAs known to date. Since their discovery 50 years ago, viroids have been considered valuable systems for the study of the structure-function relationships in RNA, essentially because they have not been shown to have coding capacity. We used two pathogenic circRNAs (Hop stunt viroid and Eggplant latent viroid) as …