We derive an efficient method for the insertion of structured particles in grand canonical Monte Carlo simulations of adsorption in very confining geometries. We extend this method to path integral simulations and use it to calculate the isotherm of adsorption of hydrogen isotopes in narrow carbon nanotubes (2D confinement) and slit pores (1D confinement) at the temperatures of 20 K and 77 K, discussing its efficiency by comparison to the standard path integral grand canonical Monte Carlo algorithm. We use this algorithm to perform multicomponent simulations in order to calculate the hydrogen isotope selectivity for adsorption in narrow carbon nanotubes and slit pores at finite pressures. The algorithm described here can be applied to the study of adsorption of real oligomers and polymers in narrow pores and channels.
Grand canonical and canonical ensembles become equivalent in the thermodynamic limit, but when the system size is finite the results obtained in the two ensembles deviate from each other. In many important cases, the canonical ensemble provides an appropriate physical description but it is often much easier to perform the calculations in the corresponding grand canonical ensemble. We present a method to compute averages in canonical ensemble based on calculations of the expectation values in grand canonical ensemble. The number of particles, which is fixed in the canonical ensemble, is not nec…
We study the grand-canonical ensemble with a fluctuating number of degrees of freedom in the context of generalized thermostatistics. Several choices of grand-canonical entropy functional are considered. The ideal gas is taken as an example.
We use the maximum information principle to include particle-interaction into the grand-canonical theory of BECs. The inclusion of the particle-interaction elucidates why thermodynamic calculations for BECs by the grand-canonical ensemble for the non-interacting case are in coincidence with up to date experimental results. However, in our generalized theory we can show that a BEC experiences a real and abrupt phase-transition in contrast to the smooth phase-transition predicted by the non-interacting grand-canonical ensemble. In addition, we discuss possible effects due to a thermal environmen…
Starting from Bloch equation for a canonical ensemble, we deduce a set of hierarchy equations for the reduced statistical density operator for an identical many-body system with two-body interaction. They provide a law according to which the reduced density operator varies in temperature. By definition of the reduced density operator in Fock space for a grand canonical ensemble, we also obtain the analogous Bloch equation and the corresponding hierarchy reduced equations for the identical interacting many-body system. We discuss their possible solutions and applications.
We describe the adaptive resolution multiscale method AdResS. The conceptual evolution as well as the improvements of its technical efficiency are described step by step, with an explicit reference to current limitations and open problems.
The one-dimensional Asymmetric Exclusion Process (ASEP) is a paradigm for nonequilibrium dynamics, in particular driven diffusive processes. It is usually considered in a canonical ensemble in which the number of sites is fixed. We observe that the grand-canonical partition function for the ASEP is remarkably simple. It allows a simple direct derivation of the asymptotics of the canonical normalization in various phases and of the correspondence with One-Transit Walks recently observed by Brak et.al.
Grand-canonical fluctuations of Bose-Einstein condensates of light are accessible to state-of-the-art experiments [J. Schmitt et al., Phys. Rev. Lett. 112, 030401 (2014).]. We phenomenologically describe these fluctuations by using the grand-canonical ensemble for a weakly interacting Bose gas at thermal equilibrium. For a two-dimensional harmonic trap, we use two models for which the canonical partition functions of the weakly interacting Bose gas are given by exact recurrence relations. We find that the grand-canonical condensate fluctuations for weakly interacting Bose gases vanish at zero …
We present a practical analysis of the fermion sign problem in fermionic path integral Monte Carlo (PIMC) simulations in the grand-canonical ensemble (GCE). As a representative model system, we consider electrons in a $2D$ harmonic trap. We find that the sign problem in the GCE is even more severe than in the canonical ensemble at the same conditions, which, in general, makes the latter the preferred option. Despite these difficulties, we show that fermionic PIMC simulations in the GCE are still feasible in many cases, which potentially gives access to important quantities like the compressibl…
We introduce a nonequilibrium grand-canonical ensemble defined by considering the stationary state of a driven system of particles put in contact with a nonequilibrium particle reservoir. At odds with its equilibrium counterpart, or with purely formal constructions of a grand-canonical ensemble, this physically-motivated construction yields a grand-canonical distribution that depends on the details of the contact dynamics between the system and the reservoir. For non-interacting driven particles, a grand-canonical chemical potential can still be defined, although this chemical potential now di…
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…
We introduce a simple but efficient method for grand-canonical twist averaging in quantum Monte Carlo calculations. By evaluating the thermodynamic grand potential instead of the ground state total energy, we greatly reduce the sampling errors caused by twist-dependent fluctuations in the particle number. We apply this method to the electron gas and to metallic lithium, aluminum, and solid atomic hydrogen. We show that, even when using a small number of twists, grand-canonical twist averaging of the grand potential produces better estimates of ground state energies than the widely used canonic…
The critical behavior of a hybrid spin-electron model with localized Ising spins placed on nodal sites and mobile electrons delocalized over bonds between two nodal lattice sites is analyzed by the use of a generalized decoration-iteration transformation. Our attention is primarily concentrated on a rigorous analysis of a critical temperature in canonical and grand-canonical statistical ensemble at two particular electron concentrations, corresponding to a quarter ($ρ\!=\!1$) and a half ($ρ\!=\!2$) filled case. It is found that the critical temperature of the investigated spin-electron system …
We present a method to facilitate Monte Carlo simulations in the grand canonical ensemble given a target mean particle number. The method imposes a fictitious dynamics on the chemical potential, to be run concurrently with the Monte Carlo sampling of the physical system. Corrections to the chemical potential are made according to time-averaged estimates of the mean and variance of the particle number, with the latter being proportional to thermodynamic compressibility. We perform a variety of tests, and in all cases find rapid convergence of the chemical potential -- inexactness of the tuning …
In the present paper, the Tsallis statistics in the grand canonical ensemble was reconsidered in a general form. The thermodynamic properties of the nonrelativistic ideal gas of hadrons in the grand canonical ensemble was studied numerically and analytically in a finite volume and the thermodynamic limit. It was proved that the Tsallis statistics in the grand canonical ensemble satisfies the requirements of the equilibrium thermodynamics in the thermodynamic limit if the thermodynamic potential is a homogeneous function of the first order with respect to the extensive variables of state of the…
Monte-Carlo sampling of lattice model Hamiltonians is a well-established technique in statistical mechanics for studying the configurational entropy of crystalline materials. When species to be distributed on the lattice model carry charge, the charge balance constraint on the overall system prohibits single-site Metropolis exchanges in MC. In this article, we propose two methods to perform MC sampling in the grand-canonical ensemble in the presence of a charge-balance constraint. The table-exchange method (TE) constructs small charge-conserving excitations, and the square-charge bias method (…
We introduce a quantum Monte Carlo method at finite temperature for interacting fermionic models in the canonical ensemble, where the conservation of the particle number is enforced. Although general thermodynamic arguments ensure the equivalence of the canonical and the grand-canonical ensembles in the thermodynamic limit, their approach to the infinite-volume limit is distinctively different. Observables computed in the canonical ensemble generically display a finite-size correction proportional to the inverse volume, whereas in the grand-canonical ensemble the approach is exponential in the…
Relation between grand canonical ensemble, Boltzmann, Fermi-Dirac, and Bose-Einstein distribution: Quantum principle for bosons and bosonic vacuum state, a candidate for dark energy and dark matter
Focusing on the grand-canonical extension of the ordinary restricted Boltzmann machine, we suggest an energy-based model for feature extraction that uses a layer of hidden units with varying size. By an appropriate choice of the chemical potential and given a sufficiently large number of hidden resources the generative model is able to efficiently deduce the optimal number of hidden units required to learn the target data with exceedingly small generalization error. The formal simplicity of the grand-canonical ensemble combined with a rapidly converging ansatz in mean-field theory enable us to…
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 cano…
We investigate the phase diagram of a three-component system of particles on a one-dimensional filled lattice, or equivalently of a one-dimensional three-state Potts model, with reflection asymmetric mean field interactions. The three types of particles are designated as $A$, $B$, and $C$. The system is described by a grand canonical ensemble with temperature $T$ and chemical potentials $Tλ_A$, $Tλ_B$, and $Tλ_C$. We find that for $λ_A=λ_B=λ_C$ the system undergoes a phase transition from a uniform density to a continuum of phases at a critical temperature $\hat T_c=(2π/\sqrt3)^{-1}$. For othe…
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…
We solve a model of polymers represented by self-avoiding walks on a lattice which may visit the same site up to three times in the grand-canonical formalism on the Bethe lattice. This may be a model for the collapse transition of polymers where only interactions between monomers at the same site are considered. The phase diagram of the model is very rich, displaying coexistence and critical surfaces, critical, critical endpoint and tricritical lines, as well as a multicritical point. From the grand-canonical results, we present an argument to obtain the properties of the model in the canonica…
A hierarchical equations of motion formalism for a quantum dissipation system in a grand canonical bath ensemble surrounding is constructed, on the basis of the calculus-on-path-integral algorithm, together with the parametrization of arbitrary non-Markovin bath that satisfies fluctuation-dissipation theorem. The influence functionals for both the Fermion or Boson bath interaction are found to be of the same path-integral expression as the canonical bath, assuming they all satisfy the Gaussian statistics. However, the equation of motion formalism are different, due to the fluctuation-dissipati…
This letter describes a novel approach for determining the surface tension of a model system that is applicable over the entire liquid-vapor coexistence region. At the heart of the method is a new technique for determining coexistence properties that utilizes transition probabilities of attempted Monte Carlo moves during a grand canonical simulation. Finite-size scaling techniques are implemented to determine the infinite system surface tension from a series of finite-size simulations. To demonstrate the new method, the surface tension of the Lennard-Jones fluid is determined at temperatures r…
It was recently shown by Bartelmann et al. how correlated initial conditions can be introduced into the statistical field theory for classical particles pioneered by Das and Mazenko. In this paper we extend this development from the canonical to the grand canonical ensemble for a system satisfying statistical homogeneity and isotropy. We do this by translating the probability distribution for the initial phase space coordinates of the particles into an easy diagrammatic representation and then using a variant of the Mayer cluster expansion to sum over particle numbers. The grand canonical gene…
The large surface density changes associated with the (100) noble metals surface hex-reconstruction suggest the use of non-particle conserving simulation methods. We present an example of a surface Grand Canonical Monte Carlo applied to the transformation of a square non reconstructed surface to the hexagonally covered low temperature stable Au(100). On the other hand, classical Molecular Dynamics allows to investigate microscopic details of the reconstruction dynamics, and we show, as an example, retraction of a step and its interplay with the surface reconstruction/deconstruction mechanism.
In this paper, the particles of quantum gases, that is, bosons and fermions are regarded as g-ons which obey fractional exclusion statistics. With this point of departure the thermostatistical relations concerning the Bose and Fermi systems are unified under the g-on formulation where a fractal approach is adopted. The fractal inspired entropy, the partition function, distribution function, the thermodynamics potential and the total number of g-ons have been found for a grand canonical g-on system. It is shown that from the g-on formulation; by a suitable choice of the parameters of the nonext…
We calculate the exact analytical coefficients of the $β$ expansion of the grand-canonical partition function of the unidimensional Hubbard model up to order $β^5$, using an alternative method, based on properties of the Grassmann algebra. The results derived are non-perturbative and no restrictions on the set of parameters that characterize the model are required. By applying this method we obtain analytical results for the thermodynamical quantities, in the high-temeprature limit, for arbitrary density of electrons in the unidimensional chain.
A theoretical scheme for the treatment of an open molecular system with electrons and nuclei is proposed. The idea is based on the Grand Canonical description of a quantum region embedded in a classical reservoir of molecules. Electronic properties of the quantum region are calculated at constant electronic chemical potential equal to that of the corresponding (large) bulk system treated at full quantum level. Instead, the exchange of molecules between the quantum region and the classical environment occurs at the chemical potential of the macroscopic thermodynamic conditions. T he Grand Canon…
Ab initio calculations and statistical mechanics are combined to elucidate the thermodynamics of H vacancies in MgH2. A general method based on a grand-canonical ensemble of defect configurations is introduced to model the exchange of hydrogen between crystalline MgH2 and gas-phase H2. We find that, at temperatures and hydrogen partial pressures of practical interest, MgH2 is capable of accommodating only very small concentrations of hydrogen vacancies, which consist mainly of isolated defects rather than vacancy clusters, contrary to what is expected from a simple energetic analysis.
We consider two different problems involving the localization of a single polymer chain: (i) a periodic $AB$ copolymer at a selective fluid-fluid interface, with the upper (resp. lower) fluid attracting $A$ (resp. $B$) monomers (ii) a homopolymer chain attracted to a hard wall (wetting). Self avoidance is neglected in both models, which enables us to study their localization transition in a grand canonical approach. We recover the results obtained in previous studies via transfer matrix methods. Moreover, we calculate in this way the loop length distribution functions in the localized phase. S…
We describe a Monte Carlo scheme for the grand canonical simulation study of fluid phase equilibria in highly size-asymmetrical binary mixtures. The method utilizes an expanded ensemble in which the insertion and deletion of large particles is accomplished {\em gradually} by traversing a series of states in which a large particle interacts only partially with the environment of small particles. Free energy barriers arising from interfacial coexistence states are surmounted with the aid of multicanonical preweighting, the associated weights being determined from the transition matrix. As an ill…
In this work, we provide a detailed theoretical analysis, supported by numerical tests, of the reliability of the adaptive resolution simulation (AdResS) technique in sampling the Grand Canonical ensemble. We demonstrate that the correct density and radial distribution functions in the hybrid region, where molecules change resolution, are two necessary conditions for considering the atomistic and coarse-grained regions in AdResS equivalent to subsystems of a full atomistic system with an accuracy up to the second order with respect to the probability distribution of the system. Moreover, we sh…
Based on the density matrix renormalization group (DMRG), strongly correlated quantum many-body systems at finite temperatures can be simulated by sampling over a certain class of pure matrix product states (MPS) called minimally entangled typical thermal states (METTS). When a system features symmetries, these can be utilized to substantially reduce MPS computation costs. It is conceptually straightforward to simulate canonical ensembles using symmetric METTS. In practice, it is important to alternate between different symmetric collapse bases to decrease autocorrelations in the Markov chain …
Calculating thermodynamic potentials and observables efficiently and accurately is key for the application of statistical mechanics simulations to materials science. However, naive Monte Carlo approaches, on which such calculations are often dependent, struggle to scale to complex materials in many state-of-the-art disciplines such as the design of high entropy alloys or multicomponent catalysts. To address this issue, we adapt sampling tools built upon machine-learning based generative modeling to the materials space by transforming them into the semi-grand canonical ensemble. Furthermore, we…
The partition function for a canonical ensemble of 2D Coulomb charges in a background potential (the Dyson gas) is realized as a vacuum expectation value of a group-like element constructed in terms of free fermionic operators. This representation provides an explicit identification of the partition function with a tau-function of the 2D Toda lattice hierarchy. Its dispersionless (quasiclassical) limit yields the tau-function for analytic curves encoding the integrable structure of the inverse potential problem and parametric conformal maps. A similar fermionic realization of partition functio…
We discuss two new DoS approaches for finite density lattice QCD. The paper extends a recent presentation of the new techniques based on Wilson fermions, while here we now discuss and test the case of finite density QCD with staggered fermions. The first of our two approaches is based on the canonical formulation where observables at a fixed net quark number $N$ are obtained as Fourier moments of the vacuum expectation values at imaginary chemical potential $θ$. We treat the latter as densities which can be computed with the recently developed FFA method. The second approach is based on a dire…
A finite-temperature many-body perturbation theory is presented that expands in power series the electronic grand potential, chemical potential, internal energy, and entropy on an equal footing. Sum-over-states and sum-over-orbitals analytical formulas for the second-order perturbation corrections to these thermodynamic properties are obtained in a time-independent, nondiagrammatic, algebraic derivation, relying on the sum rules of the Hirschfelder-Certain degenerate perturbation energies in a degenerate subspace as well as nine algebraic identities for zeroth-order thermal averages of one- th…
Quantum effects due to the spatial delocalization of light atoms are treated in molecular simulation via the path integral technique. Among several methods, Path Integral (PI) Molecular Dynamics (MD) is nowadays a powerful tool to investigate properties induced by spatial delocalization of atoms; however computationally this technique is very demanding. The abovementioned limitation implies the restriction of PIMD applications to relatively small systems and short time scales. One possible solution to overcome size and time limitation is to introduce PIMD algorithms into the Adaptive Resolutio…
A Grand-canonical Monte-Carlo simulation method extended to simulate a mixture of salts is presented. Due to charge neutrality requirement of electrolyte solutions, ions must be added to or removed from the system in groups. This leads to some complications compared to regular Grand Canonical simulation. Here, a recipe for simulation of electrolyte solution of salt mixture is presented. It is then implemented to simulate solution of 1:1, 2:1 and 2:2 salts or their mixtures at different concentrations using the primitive ion model. The osmotic pressures of the electrolyte solutions are calculat…
The thermodynamics for a system with given temperature, density, and volume is described by the Canonical ensemble. The thermodynamics for a corresponding system with the same temperature, volume, and average density is described by the Grand Canonical ensemble. In general a chosen thermodynamic potential (e.g., free energy) is different in the two cases. Their relationship is considered here as a function of the system size. Exact expressions relating the fundamental potential for each (free energy and pressure, respectively) are identified for arbitrary system size. A formal asymptotic analy…
We present a novel derivation of the constraints required to obtain the underlying principles of statistical mechanics using a maximum entropy framework. We derive the mean value constraints by use of the central limit theorem and the scaling properties of Lagrange multipliers. We then arrive at the same result using a quantum free field theory and the Ward identities. The work provides a principled footing for maximum entropy methods in statistical physics, adding the body of work aligned to Jaynes's vision of statistical mechanics as a form of inference rather than a physical theory dependen…
We report a numerical evidence that the string tension σcan be viewed as an order parameter of the phase transition, which separates the smooth phase from the crumpled one, in the fluid surface model of Helfrich and Polyakov-Kleinert. The model is defined on spherical surfaces with two fixed vertices of distance L. The string tension σis calculated by regarding the surface as a string connecting the two points. We find that the phase transition strengthens as L is increased, and that σvanishes in the crumpled phase and non-vanishes in the smooth phase.
We investigate the isobar of an ideal Bose gas confined in a cubic box within the grand canonical ensemble, for a large yet finite number of particles, N. After solving the equation of the spinodal curve, we derive precise formulae for the supercooling and the superheating temperatures which reveal an N^{-1/3} or N^{-1/4} power correction to the known Bose-Einstein condensation temperature in the thermodynamic limit. Numerical computations confirm the accuracy of our analytical approximation, and further show that the isobar zigzags on the temperature-volume plane if N is greater than or equal…
Simulation within the grand canonical ensemble is the method of choice for accurate studies of first order vapour-liquid phase transitions in model fluids. Such simulations typically employ sampling that is biased with respect to the overall number density in order to overcome the free energy barrier associated with mixed phase states. However, at low temperature and for large system size, this approach suffers a drastic slowing down in sampling efficiency. The culprits are geometrically induced transitions (stemming from the periodic boundary conditions) which involve changes in droplet shape…
The cornerstone of statistical mechanics of complex networks is the idea that the links, and not the nodes, are the effective particles of the system. Here we formulate a mapping between weighted networks and lattice gasses, making the conceptual step forward of interpreting weighted links as particles with a generalised coordinate. This leads to the definition of the grand canonical ensemble of weighted complex networks. We derive exact expressions for the partition function and thermodynamic quantities, both in the cases of global and local (i.e., node-specific) constraints on density and me…
A comprehensive and detailed account is presented for the finite-temperature many-body perturbation theory for electrons that expands in power series all thermodynamic functions on an equal footing. Algebraic recursions in the style of the Rayleigh-Schrödinger perturbation theory are derived for the grand potential, chemical potential, internal energy, and entropy in the grand canonical ensemble and for the Helmholtz energy, internal energy, and entropy in the canonical ensemble, leading to their sum-over-states analytical formulas at any arbitrary order. For the grand canonical ensemble, thes…
We present a spherical version of the grand-canonical minority game (GCMG), and solve its dynamics in the stationary state. The model displays several types of transitions between multiple ergodic phases and one non-ergodic phase. We derive analytical solutions, including exact expressions for the volatility, throughout all ergodic phases, and compute the phase behaviour of the system. In contrast to conventional GCMGs, where the introduction of memory-loss precludes analytical approaches, the spherical model can be solved also when exponential discounting is taken into account. For the case o…
A new numerical algorithm for interacting fermion systems to treat the grand-canonical ensemble is proposed and examined by extending the path-integral renormalization group method. To treat the grand-canonical ensemble, the particle-hole transformation is applied to the Hamiltonian and basis states. In the interaction-term projection, the Stratonovich-Hubbard transformation which hybridizes up and down spin electrons is introduced. By using this method, the phase diagram of the two-dimensional Hubbard model with next-nearest-neighbor transfer is accurately determined by treating the filling-c…
A classical density functional theory (cDFT) based on the PC-SAFT equation of state is proposed for the calculation of adsorption equilibria of pure substances and their mixtures in covalent organic frameworks (COFs). Adsorption isotherms of methane, ethane, n-butane and nitrogen in the COFs TpPa-1 and 2,3-DhaTph are calculated and compared to results from grand canonical Monte Carlo (GCMC) simulations. Mixture adsorption is investigated for the methane/ethane and methane/n-butane binary systems. Excellent agreement between PC-SAFT DFT and GCMC is obtained for all adsorption isotherms up to pr…
The equilibrium density distribution and thermodynamic properties of a Lennard-Jones fluid confined to nano-sized spherical cavities at constant chemical potential was determined using Monte Carlo simulations. The results describe both a single cavity with semipermeable walls as well as a collection of closed cavities formed at constant chemical potential. The results are compared to calculations using classical Density Functional Theory (DFT). It is found that the DFT calculations give a quantitatively accurate description of the pressure and structure of the fluid. Both theory and simulation…
We describe a Monte Carlo scheme for simulating polydisperse fluids within the grand canonical ensemble. Given some polydisperse attribute $σ$, the state of the system is described by a density distribution $ρ(σ)$ whose form is controlled by the imposed chemical potential distribution $μ(σ)$. We detail how histogram extrapolation techniques can be employed to tune $μ(σ)$ such as to traverse some particular desired path in the space of $ρ(σ)$. The method is applied in simulations of size-disperse hard spheres with densities distributed according to Schulz and log-normal forms. In each case, the…
We re-examine the way in which Bogoliubov's theory of a dilute Bose gas at $T=0$ has been extended to describe the statistical mechanics of interacting bosons at finite temperature. We show explicitly that the field-theoretic calculation of the grand partition function in this formulation amounts to a canonical trace over the eigenfunctions of the Bogoliubov Hamiltonian at fixed total number of bosons $N$, and that the additional trace over $N$ that is required in the grand-canonical formalism is never carried out. This implies that what usually passes as the grand-canonical treatment of the B…
