Search results for " ensemble"

Molecular wires - long range electron tunneling and hopping in novel donor-acceptor ensembles

2004

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 …

Elastic constants from microscopic strain fluctuations

1999

Fluctuations of the instantaneous local Lagrangian strain $\epsilon_{ij}(\bf{r},t)$, measured with respect to a static ``reference'' lattice, are used to obtain accurate estimates of the elastic constants of model solids from atomistic computer simulations. The measured strains are systematically coarse- grained by averaging them within subsystems (of size $L_b$) of a system (of total size $L$) in the canonical ensemble. Using a simple finite size scaling theory we predict the behaviour of the fluctuations $$ as a function of $L_b/L$ and extract elastic constants of the system {\em in the thermodynamic limit} at nonzero temperature. Our method is simple to implement, efficient and general e…

STRUCTURAL INSTABILITY IN FERROELECTRICS: SUPERIMPOSING HAMILTONIAN AND STOCHASTIC DYNAMICS

2008

ABSTRACT Structural instability of ferroelectrics distinguished by appearance of coexisting phases and spatial inhomogeneity is at variance with the predictions of statistics in the canonical ensemble. A more refined description includes ergodicity breaking which become apparent at critical temperature when the system resides in metastable state and its development lead to one of possible minimum energy states. In this study the domain growth and switching is reproduced within the framework of Fokker-Planck approach. The mathematical technique is developed for empiric Landau Hamiltonians and improved for application to first principles effective Hamiltonians with supercells and elementary l…

Monte Carlo studies of finite-size effects at first-order transitions

1990

Abstract First-order phase transitions are ubiquitous in nature but their presence is often uncertain because of the effects which finite size has on all transitions. In this article we consider a general treatment of size effects on lattice systems with discrete degrees of freedom and which undergo a first-order transition in the thermodynamic limit. We review recent work involving studies of the distribution functions of the magnetization and energy at a first-order transition in a finite sample of size N connected to a bath of size N′. Two cases: N′ = ∞ and N′ = finite are considered. In the former (canonical ensemble) case, the distributions are approximated by a superposition of Gaussi…

Constant potential rate theory – general formulation and electrocatalysis

2021

Exercises, Hints and Selected Solutions

2016

1.1. Prove the formula (1.8a) in Sect. 1.3, $$\displaystyle{ \int \mathrm{d}^{n}x\; =\int _{ 0}^{+\infty }\!\!\!\mathrm{d}r\;r^{n-1}\int _{ 0}^{2\pi }\!\!\!\mathrm{d}\phi \prod _{ k=1}^{n-2}\int _{ 0}^{\pi }\!\!\!\mathrm{d}\theta _{ k}\sin ^{k}(\theta _{ k}) }$$ (1.1) by means of induction.

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".