Subscribe to the gold package and get unlimited access to Shamra Academy
Register a new userClassical Density Functional Theory in the Canonical Ensemble
237
0
0.0
(
0
)
Authors
James F. Lutsko
Ask ChatGPT about the research
No Arabic abstract
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.
rate research
Read More
We derive the second-order approximation (PT2) to the ensemble correlation energy functional by applying the G{o}rling-Levy perturbation theory on the ensemble density-functional theory (EDFT). Its performance is checked by calculating excitation energies with the direct ensemble correction method in 1D model systems and 3D atoms using numerically exact Kohn-Sham orbitals and potentials. Comparing with the exchange-only approximation, the inclusion of the ensemble PT2 correlation improves the excitation energies in 1D model systems in most cases, including double excitations and charge-transfer excitations. However, the excitation energies for atoms are generally worse with PT2. We find that the failure of PT2 in atoms is due to the two contributions of an orbital-dependent functional to excitation energies being inconsistent in the calculations. We also analyze the convergence of PT2 excitation energies with respect to the number of unoccupied orbitals.
We construct a density functional for the lattice gas / Ising model on square and cubic lattices based on lattice fundamental measure theory. In order to treat the nearest-neighbor attractions between the lattice gas particles, the model is mapped to a multicomponent model of hard particles with additional lattice polymers where effective attractions between particles arise from the depletion effect. The lattice polymers are further treated via the introduction of polymer clusters (labelled by the numbers of polymer they contain) such that the model becomes a multicomponent model of particles and polymer clusters with nonadditive hard interactions. The density functional for this nonadditive hard model is constructed with lattice fundamental measure theory. The resulting bulk phase diagram recovers the Bethe-Peierls approximation and planar interface tensions show a considerable improvement compared to the standard mean-field functional and are close to simulation results in three dimensions. We demonstrate the existence of planar interface solutions at chemical potentials away from coexistence when the equimolar interface position is constrained to arbitrary real values.
We present a self-contained theory for the exact calculation of particle number counting statistics of non-interacting indistinguishable particles in the canonical ensemble. This general framework introduces the concept of auxiliary partition functions, and represents a unification of previous distinct approaches with many known results appearing as direct consequences of the developed mathematical structure. In addition, we introduce a general decomposition of the correlations between occupation numbers in terms of the occupation numbers of individual energy levels, that is valid for both non-degenerate and degenerate spectra. To demonstrate the applicability of the theory in the presence of degeneracy, we compute energy level correlations up to fourth order in a bosonic ring in the presence of a magnetic field.
The chemical ordering transition in a binary alloy is examined using classical density functional theory for a binary mixture. The ordered lattice is assumed to be obtained from the disordered lattice by a volume change only, as in L1_2 ordering from an face centered cubic chemically disordered crystal. Using the simplest possible approach, second order truncation of the expansion, non-overlapping Gaussian distributions at the sites, and expansion of the correlation functions about the sites, a very tractable expansion is obtained. Under these assumptions the expansion consists of the same terms as the lattice gas formalism where the lattice is implicitly taken as fixed, plus additional interaction terms, and an additional entropy term. This additional entropy term represents a lowest order approximation to the vibrational entropy change.
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.
Log in to be able to interact and post comments
comments
Fetching comments
Sign in to be able to follow your search criteria
