Search results for "Ensemble"

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.

Probing slow fluctuations in nonergodic systems: Interleaved sampling technique

2007

We present a new dynamic light scattering scheme to obtain ensemble-averaged correlation functions of slow fluctuations in non-ergodic systems in an efficient way. On a rotating sample, a large set of separate correlation functions is measured in parallel, for each independent orientational component of the sample’ density fluctuations. The ensemble-averaged correlation function spans a lag time range from 1 to 104 s. We describe our first implementation of this technique, discuss its statistical accuracy and show first results. Compared to plain ensemble averaging over a series of N measurements, the total measurement time is usualy reduced by a factor N without significant degradation of …

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…

Phänomenologische Betrachtung zur Photon-Elektron-Wechselwirkung in einem Plasma

1961

The question at stake is, whether a simple physical connection may be found between Richardson equation for thermionic emission on the one hand, and Richardson equation for photoelectric emission on the other hand. The proposition of such a connection is based on the following supposition: that electrons are not only elements of a (Fermi-Dirac-) statistical ensemble and, as such, cause thermionic phenomena; but that they can also interact with a radiation field, thereby causing an additional emission current, according to Richardson (photoelectric) equation. — It is shown in detail that the current emitted from a metal of 2000 °K is determined by the complete radiation of this metal only to…

Free-energy barriers for crystal nucleation from fluid phases.

2017

Monte Carlo simulations of crystal nuclei coexisting with the fluid phase in thermal equilibrium in finite volumes are presented and analyzed, for fluid densities from dense melts to the vapor. Generalizing the lever-rule for two-phase coexistence in the canonical ensemble to finite volume, "measurements" of the nucleus volume together with the pressure and chemical potential of the surrounding fluid allows to extract the surface free energy of the nucleus. Neither the knowledge of the (in general non-spherical) nucleus shape nor of the angle-dependent interface tension is required for this task. The feasibility of the approach is demonstrated for a variant of the Asakura-Oosawa model for c…

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…