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 show that the work done by the thermostat and a thermodynamic force in the transition region is formally equivalent to balance the chemical potential difference between the different resolutions. From these results follows the main conclusion that the atomistic region exchanges molecules with the coarse-grained region in a Grand Canonical fashion with an accuracy up to (at least) second order. Numerical tests, for the relevant case of liquid water at ambient conditions, are carried out to strengthen the conclusions of the theoretical analysis. Finally, in order to show the computational convenience of AdResS as a Grand Canonical set up, we compare our method to the Insertion Particle Method (IMP) in its most efficient computational implementation. This fruitful combination of theoretical principles and numerical evidence candidates the adaptive resolution technique as a natural, general and efficient protocol for Grand Canonical Molecular Dynamics for the case of large systems.
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…
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…
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 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…
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 …
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…
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…
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…
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…
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…
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…
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…
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…
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 …
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…
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…
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 (…
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…
Precise Determination of Phase Diagram for Two-Dimensional Hubbard Model with Filling- and Bandwidth-Control Mott Transitions: Grand-Canonical Path-Integral Renormalization Group Approach
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…
Liouville's theorem in a grand ensemble, that is for situations where a system is in equilibrium with a reservoir of energy and particles, is a subject that, to our knowledge, has not been explicitly treated in literature related to molecular simulation. Instead Liouville's theorem, a central concept for the correct employment of molecular simulation techniques, is implicitly considered only within the framework of systems where the total number of particles is fixed. However the pressing demand of applied science in treating open systems leads to the question of the existence and possible exa…
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…
