Grand Canonical Ensemble Research Articles

Canonical vs. Grand Canonical Ensemble for Bosonic Gases under Harmonic Confinement

We analyze the general relation between canonical and grand canonical ensembles in the thermodynamic limit. We begin our discussion by deriving, with an alternative approach, some standard results first obtained by Kac and coworkers in the late 1970s. Then, motivated by the Bose–Einstein condensation (BEC) of trapped gases with a fixed number of atoms, which is well described by the canonical ensemble and by the recent groundbreaking experimental realization of BEC with photons in a dye-filled optical microcavity under genuine grand canonical conditions, we apply our formalism to a system of non-interacting Bose particles confined in a two-dimensional harmonic trap. We discuss in detail the mathematical origin of the inequivalence of ensembles observed in the condensed phase, giving place to the so-called grand canonical catastrophe of density fluctuations. We also provide explicit analytical expressions for the internal energy and specific heat and compare them with available experimental data. For these quantities, we show the equivalence of ensembles in the thermodynamic limit.

Chemical reaction process and dynamic characteristics of urea pyrolysis products in inhibiting gas explosion

During the coal mining process, gas explosions pose significant hazards, causing casualties and property losses. In order to develop new types of inhibitors for gas explosions, this paper explores the reaction mechanisms of urea pyrolysis products NH3 and HNCO inhibiting gas explosions based on density functional theory (DFT), transition state theory, and grand canonical ensemble Monte Carlo method (GCMC). It analyzes the reaction processes and kinetic characteristics of urea pyrolysis products with key radicals and gas molecules involved in explosions from a microscopic dynamic perspective. The results show that urea pyrolysis products exhibit good inhibition effects on active radicals involved in explosion reactions·NH3 and HNCO show stronger van der Waals forces in electrostatic attraction towards O2 and *H, respectively, and faster rate advantages in reaction rate constants. The lower Gibbs free energy barrier indicates higher reaction activity of pyrolysis products, thereby diluting the concentration of key radicals involved in explosion reactions and effectively inhibiting explosion key elementary reactions (R32, R38, R53, R57, R156, and R170). This study provides new insights into the microscopic inhibition mechanism of urea pyrolysis products on gas explosions, offering a new approach for designing more targeted modified inhibitors, which helps reduce the hazards of gas explosions during coal mining and provides scientific support and technical guidance for safe coal mining production.

Redox properties of PbO2, IrO2 and SnO2 (110) surfaces with an adsorbed OH molecule: a chemical reactivity study in the grand canonical ensemble

Redox properties of PbO2, IrO2 and SnO2 (110) surfaces with an adsorbed OH molecule: a chemical reactivity study in the grand canonical ensemble

Molecular modeling of CO2 affecting competitive adsorption within anthracite coal

This study aimed to investigate the adsorption properties of CO2, CH4, and N2 on anthracite. A molecular structural model of anthracite (C208H162O12N4) was established. Simulations were performed for the adsorption properties of single-component and multi-component gases at various temperatures, pressures, and gas ratios. The grand canonical ensemble Monte Carlo approach based on molecular mechanics and dynamics theories was used to perform the simulations. The results showed that the isotherms for the adsorption of single-component CO2, CH4, and N2 followed the Langmuir formula, and the CO2 adsorption isotherm growth gradient was negatively correlated with pressure but positively correlated with temperature. When the CO2 injection in the gas mixture was increased from 1 to 3% for the multi-component gas adsorption, the proportion of CO2 adsorption rose from 1/3 to 2/3, indicating that CO2 has a competing-adsorption advantage. The CO2 adsorption decreased faster with increasing temperature, indicating that the sensitivity of CO2 to temperature is stronger than that of CH4 and N2. The adsorbent potential energies of CO2, CH4, and N2 diminished with rising temperature in the following order: CO2 < CH4 < N2.

From clusters of moving molecules to continua: Material elements as open systems

We discuss the discrete-to-continuum transition in the description of matter, starting from a cluster of flowing molecules with equal mass and ending up with a non-simple fluid. We account for the fluctuations beyond a local affine approximation of the velocity distribution of molecules within a space window adopted to compute some prominent statistics. The resulting continuum picture accounts for local mass variation in each space window corresponding to a point in the continuum scale. From a statistical viewpoint, every material element is thus considered as a grand-canonical ensemble. So-called C-derivatives account for macroscopic-to-mesoscopic relative motion. When considered for second-rank tensors, they extend Truesdell’s derivative and reduce to Oldroyd’s one when the macroscopic-to-mesoscopic relative motion vanishes. Fluctuations beyond an affine component best approximating the kinetic energy are summarized into a second-rank symmetric tensor whose time variation enters a balance equation governing transfer from velocity fluctuations to heat. Eventually, we discuss essential elements of thermodynamics in the present setting. What emerges is the possibility of a non-Fourier type heat transfer. The results address computational schemes for field representations of sparse phase dynamics, such as granular materials, and the one of bodies with transport of scattered molecules, such as pollutants in fluids or proteins in biological tissues.

Casimir and Helmholtz forces in one-dimensional Ising model with Dirichlet (free) boundary conditions

Attention in the literature has increasingly turned to the issue of the dependence on ensemble and boundary conditions of fluctuation-induced forces. We have recently investigated this problem in the one-dimensional Ising model with periodic and antiperiodic boundary conditions (Annals of Physics 459, 169533 (2023)). Significant variations of the behavior of Casimir and Helmholtz forces was observed, depending on both ensemble and boundary conditions. Here we extend our study by considering the problem in the important case of Dirichlet (also termed free, or missing neighbors) boundary conditions. The advantage of the mathematical formulation of the problem in terms of Chebyshev polynomials is demonstrated and, in this approach, expressions for the partition functions in the canonical and the grand canonical ensembles are presented. We prove analytically that the Casimir force is attractive for all values of temperature and external ordering field, while the Helmholtz force can be both attractive and repulsive.

Topology of critical points in boundary matrix duals

Computation of topological charges of the Schwarzschild and charged black holes in AdS in canonical and grand canonical ensembles allows for a classification of the phase transition points via the Bragg-Williams off-shell free energy. We attempt a topological classification of the critical points and the equilibrium phases of the dual gauge theory via a phenomenological matrix model, which captures the features of the \\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\mathcal{N}$$\\end{document} = 4, SU(N) Super Yang-Mills theory on S3 at finite temperature at large N. With minimal modification of parameters, critical points of the matrix model at finite chemical potential can be classified as well. The topological charges of locally stable and unstable dynamical phases of the system turn out to be opposite to each other, totalling to zero, and this matches the analysis in the bulk.

Effect of zero-point motion on properties of quantum particles adsorbed on a substrate

We qualitatively investigate the effect of zero-point motion (ZPM) on the structure and properties of a film composed of quantum particles adsorbed on a graphite substrate. The amplitude of ZPM is controlled by a change of the particle mass while keeping the interactions fixed. In that sense it is assumed that the interactions can be controlled by future doping methods. The worm-algorithm path integral Monte Carlo (WAPIMC) method is applied to simulate this system in the grand-canonical ensemble, where particles can be exchanged with the external particle reservoir. Another method, namely the multiconfigurational time-dependent Hartree method for bosons is additionally applied to verify some of the WAPIMC results and to provide further information on the entropy and the condensate fraction. Several important findings are reported. It is found that ZPM plays an important role in defining order and disorder in the crystalline structure of the adsorbed film. The total energy of the film drops with a reduction in the amplitude of ZPM, that is, it becomes more negative which is an indication to stronger adsorption. For a few particle numbers, a significant condensate fraction is detected that however drops sharply at critical values of the ZPM amplitude. Most importantly, a connection is established between chaos, in coordinate as well as momentum space, and the Heisenberg uncertainty principle. The importance of the present study lies in the fact that adsorbed two-dimensional films serve as an excellent experimental testbed for demonstrating low-dimensional quantum phenomena in the ground state. The present examination contributes also to a further understanding of the properties of heavy quantum particles adsorbed on substrates.

Being heterogeneous is disadvantageous: Brownian non-Gaussian searches.

Diffusing diffusivity models, polymers in the grand canonical ensemble and polydisperse, and continuous-time random walks all exhibit stages of non-Gaussian diffusion. Is non-Gaussian targeting more efficient than Gaussian? We address this question, central to, e.g., diffusion-limited reactions and some biological processes, through a general approach that makes use of Jensen's inequality and that encompasses all these systems. In terms of customary mean first-passage time, we show that Gaussian searches are more effective than non-Gaussian ones. A companion paper argues that non-Gaussianity becomes instead highly more efficient in applications where only a small fraction of tracers is required to reach the target.

The isoscaling properties for neutron-rich fragments in very asymmetric heavy ion collision systems

Abstract Historically, isoscaling has often been understood and applied under the grand canonical ensemble, assuming that the fragments are produced after the statistical equilibrium state is achieved. However, the influence of the symmetry energy may lead to differences in the neutron and density distribution in neutron-rich nuclei, potentially impacting the isoscaling parameters (usually denoted by $\alpha$ and $\beta$. We study the isoscaling properties for neutron-rich fragments produced in very asymmetric systems on inverse kinematics, namely $^{40,48}$Ca and $^{58,64}$Ni + $^{9}$Be at 140 MeV per nucleon. We evaluate the $\alpha$ and $\beta$ value and sort them as a function of the neutron excess $I \equiv N-Z$. The significant differences in $\alpha$ extracted from fragments within different range of $I$ emphasize the importance of understanding the isoscaling parameters dependence of fragments produced in different collision regions. Furthermore, the $|\beta(N)| / \alpha(Z)$ value for a specific fragment in small size and highly isospin asymmetry systems can serve as a probe to detect the variations of neutron density and proton density in different regions of the nucleus and point out the limitations of theoretical models in investigating these issues.

Confinement Effects in Droplet Formation on a Solid Particle.

Formation of a droplet around a spherical solid particle in supersaturated vapor is considered. The number and stability of equilibrium solutions in a closed small system are studied in the canonical ensemble in comparison to an open system in the grand canonical ensemble. Depending on the system's parameters, two modes exist in the canonical ensemble: the first one with only one solution and the second one with three solutions; the presence of the third solution is due to confinement. The analysis is conducted first on a macroscopic thermodynamic level of description, and then the results are supported by studies within two versions of classical density functional theory: the square-gradient approximation with the Carnahan-Starling equation of state for hard spheres on a completely wettable particle and the random-phase approximation with the fundamental measure theory on a poorly wettable particle. In the latter case, a solution breaking the spherical symmetry is observed at a small total number of molecules.

Positivity preserving density matrix minimization at finite temperatures via square root.

We present a Wave Operator Minimization (WOM) method for calculating the Fermi-Dirac density matrix for electronic structure problems at finite temperature while preserving physicality by construction using the wave operator, i.e., the square root of the density matrix. WOM models cooling a state initially at infinite temperature down to the desired finite temperature. We consider both the grand canonical (constant chemical potential) and canonical (constant number of electrons) ensembles. Additionally, we show that the number of steps required for convergence is independent of the number of atoms in the system. We hope that the discussion and results presented in this article reinvigorate interest in density matrix minimization methods.

Canonical Ensemble vs. Grand Canonical Ensemble in the Description of Multicomponent Bosonic Systems

The thermodynamics of a system of interacting bosonic particles and antiparticles in the presence of the Bose–Einstein condensate is studied in the framework of a Skyrme-like mean-field model. It is assumed that the total charge density (isospin density) is conserved at all temperatures. Two cases are explicitly considered: the zero or nonzero isospin charge of the system. A comparative analysis is carried out using the Canonical Ensemble or the Grand Canonical Ensemble. It is shown that the Grand Canonical Ensemble is not suitable for describing the bosonic systems of particles and antiparticles in the presence of a condensate, but an adequate study can be carried out within the framework of the canonical ensemble, where the chemical potential is a thermodynamic quantity that depends on the canonical free variable.

Topology of Hořava–Lifshitz black holes in different ensembles

In this paper, we study topological numbers for uncharged and charged static black holes obtained in z=3\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$z=3$$\\end{document} Hořava–Lifshitz gravity theory in different ensembles, where z measures the degree of anisotropy between space and time. We first calculate the topological numbers for the uncharged black holes by changing the value of the dynamic coupling constant, and find that the black holes with spherical and flat horizons have the same topological number. When the black hole’s horizon is hyperbolic, different values of the coupling constant generate different topological numbers, which can be 1, 0 or -1\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$-1$$\\end{document}. This shows that the coupling constant plays an important role in the topological classification. Then we study the topological numbers for the charged black holes in different ensembles. The black hole with a spherical horizon has the same topological number in canonical and grand canonical ensembles. When the horizons are flat or hyperbolic, they have different topological numbers in canonical and grand canonical ensembles. Therefore, the topological numbers for the uncharged black holes are parameter dependent, and those for the charged black holes are ensemble dependent.

Natural determinant reference functional theory.

The natural determinant reference (NDR) or principal natural determinant is the Slater determinant comprised of the N most strongly occupied natural orbitals of an N-electron state of interest. Unlike the Kohn-Sham (KS) determinant, which yields the exact ground-state density, the NDR only yields the best idempotent approximation to the interacting one-particle reduced density matrix, but it is well-defined in common atom-centered basis sets and is representation-invariant. We show that the under-determination problem of prior attempts to define a ground-state energy functional of the NDR is overcome in a grand-canonical ensemble framework at the zero-temperature limit. The resulting grand potential functional of the NDR ensemble affords the variational determination of the ground state energy, its NDR (ensemble), and select ionization potentials and electron affinities. The NDR functional theory can be viewed as an "exactification" of orbital optimization and empirical generalized KS methods. NDR functionals depending on the noninteracting Hamiltonian do not require troublesome KS-inversion or optimized effective potentials.

Ising model for the freezing transition.

We introduce a three-state Ising model with entropy-volume coupling suitably incorporating a packing mechanism into a lattice gas with no attractive interactions. On working in a great grand canonical ensemble in which the energy, volume, and number of particles are all allowed to fluctuate simultaneously, the model's mean-field solutions illuminate a strictly first-order transition akin to hard-sphere freezing while describing the thermodynamics of solid and fluid phases. Further implementation of attractive interactions in a natural way allows every aspect of the phase diagram of a simple substance to be reproduced, thereby accomplishing the van der Waals picture of the states of matter from first principles of statistical mechanics. This fairly accurate qualitative description plausibly renders mean-field theory a reasonable approach for freezing in three dimensions. At the same time, our mean-field treatment itself suggests freezing to persist in infinitely many dimensions, as advanced from recent simulations [Charbonneau et al., Eur. Phys. J. E 44, 101 (2021)10.1140/epje/s10189-021-00104-y].

Constant inner potential DFT for modelling electrochemical systems under constant potential and bias

Electrochemical systems play a decisive role in, e.g. clean energy conversion but understanding their complex chemistry remains an outstanding challenge. Constant potential and grand canonical ensemble (GCE) simulations are indispensable for unraveling the properties of electrochemical processes as a function of the electrode potential. Currently, GCE calculations performed at the density functional theory (DFT) level require fixing the Fermi level within the simulation cell. Here, we illustrate that this method is inadequate when modeling outer sphere reactions and a biased two-electrode cell. For these systems, the Fermi level obtained from DFT calculations does not accurately present the experimentally controlled electrode potential or describe the thermodynamic independent variable in GCE-DFT. To address this limitation, we developed and implemented a constant inner potential (CIP) method offering a more robust and general approach to conducting GCE-DFT simulations of electrochemical systems under constant potential or bias conditions. The primary advantage of CIP is that it uses the local electrode inner potential as the thermodynamic parameter for the electrode potential, as opposed to the global Fermi level. Through numerical and analytical studies, we demonstrate that the CIP and Fermi level GCE-DFT approaches are equivalent for metallic electrodes and inner-sphere reactions. However, CIP proves to be more versatile, as it can be applied to outer-sphere and two-electrode systems, addressing the limitations of the constant Fermi-level approach in these scenarios. Altogether, the CIP approach stands out as a general and efficient GCE-DFT method simulating electrochemical interfaces from first principles.

Perturbation theory in a microcanonical ensemble

The microcanonical ensemble is a natural starting point of statistical mechanics. However, when it comes to perturbation theory in statistical mechanics, mainly the canonical and grand canonical ensembles have been used. In this article we show how the microcanonical ensemble can be directly used to carry out perturbation theory for both non-interacting and interacting systems. We obtain the first non-trivial order answers for the specific heat of anharmonic oscillators and for the virial expansion in real gases. They are in exact agreement with the results obtained from the canonical ensemble. In addition, we show how crossover functions for the specific heat of anharmonic oscillators can be constructed using a microcanonical ensemble and also how the subsequent terms of the virial expansion can be obtained. We find that if we consider quantum free particles in a one-dimensional box of extension L, then both the ensembles give an unusual result for the first correction to the specific heat in the high temperature limit.

Equation of state of partially ionized hydrogen and deuterium plasma revisited.

We present improved first-principle fermionic path integral Monte Carlo (PIMC) simulation results for a dense partially ionized hydrogen (deuterium) plasma, for temperatures in the range 15000K≤T≤400000K and densities 7×10^{-7}g/cm^{3}≤ρ_{H}≤0.085g/cm^{3} (1.4×10^{-6}g/cm^{3}≤ρ_{D}≤0.17g/cm^{3}), corresponding to 100≥r_{s}≥2, where r_{s}=r[over ¯]/a_{B} is the ratio of the mean interparticle distance to the Bohr radius. These simulations are based on the fermionic propagator PIMC (FP-PIMC) approach in the grand canonical ensemble [Filinov et al., Contrib. Plasma Phys. 61, e202100112 (2021)0863-104210.1002/ctpp.202100112] and fully account for correlation and quantum degeneracy and spin effects. For the application to hydrogen and deuterium, we develop a combination of the fourth-order factorization and the pair product ansatz for the density matrix. Moreover, we avoid the fixed node approximation that may lead to uncontrolled errors in restricted PIMC (RPIMC). Our results allow us to critically reevaluate the accuracy of the RPIMC simulations for hydrogen by Hu etal. [Phys. Rev. B 84, 224109 (2011)1098-012110.1103/PhysRevB.84.224109] and of various chemical models. The deviations are generally found to be small, but for the lowest temperature, T=15640K they reach several percent. We present detailed tables with our first principles results for the pressure and energy isotherms. We expect our updated results will serve as a valuable benchmark for comparison with other methods.

Strongly non-additive symmetric mixtures in slit-like pores

Using Monte Carlo simulation methods in the grand canonical ensemble, we have studied the behavior of symmetric binary mixtures confined between attractive planes. We have elucidated the effects of high negative geometric and energetic non-additivity on the phase behavior of mixtures in nanoscopic slit-like pores. In such systems, the geometric non-additivity favors mixing, while the energetic non-additivity favors the formation demixed dense phases. It has been shown that the confinement considerably influences the phase behavior. In particular, phase separation has been found to be suppressed in narrow pores, while in wide pores the phase behavior becomes qualitatively the same as in bulk systems. It has also been demonstrated that the demixed solid is stable over a certain temperature range in pores, while the bulk mixtures characterized by the same non-additivity exhibit only the presence of mixed solid.