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Register a new userMini-grand canonical ensemble: chemical potential in the solvation shell
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Quantifying the statistics of occupancy of solvent molecules in the vicinity of solutes is central to our understanding of solvation phenomena. Number fluctuations in small `solvation shells around solutes cannot be described within the macroscopic grand canonical framework using a single chemical potential that represents the solvent `bath. In this communication, we hypothesize that molecular-sized observation volumes such as solvation shells are best described by coupling the solvation shell with a mixture of particle baths each with its own chemical potential. We confirm our hypotheses by studying the enhanced fluctuations in the occupancy statistics of hard sphere solvent particles around a distinguished hard sphere solute particle. Connections with established theories of solvation are also discussed.
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In this paper we take a fresh look at the long standing issue of the nature of macroscopic density fluctuations in the grand canonical treatment of the Bose-Einstein condensation (BEC). Exploiting the close analogy between the spherical and mean-spherical models of magnetism with the canonical and grand canonical treatment of the ideal Bose gas, we show that BEC stands for different phenomena in the two ensembles: an ordering transition of the type familiar from ferromagnetism in the canonical ensemble and condensation of fluctuations, i.e. growth of macroscopic fluctuations in a single degree of freedom, without ordering, in the grand canonical case. We further clarify that this is a manifestation of nonequivalence of the ensembles, due to the existence of long range correlations in the grand canonical one. Our results shed new light on the recent experimental realization of BEC in a photon gas, suggesting that the observed BEC when prepared under grand canonical conditions is an instance of condensation of fluctuations.
Classical density functional theory for finite temperatures is usually formulated in the grand-canonical ensemble where arbitrary variations of the local density are possible. However, in many cases the systems of interest are closed with respect to mass, e.g. canonical systems with fixed temperature and particle number. Although the tools of standard, grand-canonical density functional theory are often used in an ad hoc manner to study closed systems, their formulation directly in the canonical ensemble has so far not been known. In this work, the fundamental theorems underlying classical DFT are revisited and carefully compared in the two ensembles showing that there are only trivial formal differences. The practicality of DFT in the canonical ensemble is then illustrated by deriving the exact Helmholtz functional for several systems: the ideal gas, certain restricted geometries in arbitrary numbers of dimensions and finally a system of two hard-spheres in one dimension (hard rods) in a small cavity. Some remarkable similarities between the ensembles are apparent even for small systems with the latter showing strong echoes of the famous exact of result of Percus in the grand-canonical ensemble.
The framework of non-extensive statistical mechanics, proposed by Tsallis, has been used to describe a variety of systems. The non-extensive statistical mechanics is usually introduced in a formal way, using the maximization of entropy. In this article we investigate the canonical ensemble in the non-extensive statistical mechanics using a more traditional way, by considering a small system interacting with a large reservoir via short-range forces. The reservoir is characterized by generalized entropy instead of the Boltzmann-Gibbs entropy. Assuming equal probabilities for all available microstates we derive the equations of the non-extensive statistical mechanics. Such a procedure can provide deeper insight into applicability of the non-extensive statistics.
We show how canonical ensemble expectation values can be extracted from quantum Monte Carlo simulations in the grand canonical ensemble. In order to obtain results for all particle sectors, a modest number of grand canonical simulations must be performed, each at a different chemical potential. From the canonical ensemble results, grand canonical expectation values can be extracted as a continuous function of the chemical potential. Results are presented from the application of this method to the two-dimensional Hubbard model.
The so-called grand canonical catastrophe of the density fluctuations in the ideal Bose gas is shown to be a particular instance of the much more general phenomenon of condensation of fluctuations, taking place in a large system, in or out of equilibrium, when a single degree of freedom makes a macroscopic contribution to the fluctuations of an extensive quantity. The pathological character of the catastrophe is demystified by emphasizing the connection between experimental conditions and statistical ensembles, as demonstrated by the recent realization of photon condensation under grand canonical conditions.
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