Particle Number Fluctuations Research Articles

Emergence of fluctuating hydrodynamics in chaotic quantum systems

A fundamental principle of chaotic quantum dynamics is that local subsystems eventually approach a thermal equilibrium state. The corresponding timescales increase with subsystem size as equilibration is limited by the hydrodynamic build-up of fluctuations on extended length scales. We perform large-scale quantum simulations that monitor particle-number fluctuations in tunable ladders of hard-core bosons and explore how the build-up of fluctuations changes as the system crosses over from integrable to fully chaotic dynamics. Our results indicate that the growth of large-scale fluctuations in chaotic, far-from-equilibrium systems is quantitatively determined by equilibrium transport coefficients, in agreement with the predictions of fluctuating hydrodynamics. This emergent hydrodynamic behaviour of subsystem fluctuations provides a test of fluctuation–dissipation relations far from equilibrium and allows the accurate determination of equilibrium transport coefficients using far-from-equilibrium quantum dynamics.

Coordinate versus momentum cuts and effects of collective flow on critical fluctuations

We analyze particle number fluctuations in the crossover region near the critical endpoint of a first-order phase transition by utilizing molecular dynamics simulations of the classical Lennard-Jones fluid. We extend our previous study [V. A. Kuznietsov , ] by incorporating longitudinal collective flow. The scaled variance of particle number distribution inside different coordinate and momentum space acceptances is computed through ensemble averaging and found to agree with earlier results obtained using time averaging, validating the ergodic hypothesis for fluctuation observables. Presence of a sizable collective flow is found to be essential for observing large fluctuations from the critical point in momentum space acceptances. We discuss our findings in the context of heavy-ion collisions. Published by the American Physical Society 2024

What is the best simulation approach for measuring local density fluctuations near solvo-/hydrophobes?

Measurements of local density fluctuations are crucial to characterizing the interfacial properties of equilibrium fluids. A specific case that has been well-explored involves the heightened compressibility of water near hydrophobic entities. Commonly, a spatial profile of local fluctuation strength is constructed from the measurements of the mean and variance of solvent particle number fluctuations in a set of contiguous subvolumes of the system adjacent to the solvo-/hydrophobe. An alternative measure proposed by Evans and Stewart [J. Phys.: Condens. Matter 27, 194111 (2015)] defines a local compressibility profile in terms of the chemical potential derivative of the spatial number density profile. Using Grand canonical Monte Carlo simulation, we compare and contrast the efficacy of these two approaches for a Lennard-Jones solvent at spherical and planar solvophobic interfaces and SPC/E water at a hydrophobic spherical solute. Our principal findings are as follows: (i) the local compressibility profile χ(r) of Evans and Stewart is considerably more sensitive to variations in the strength of local density fluctuations than the spatial fluctuation profile F(r) and can resolve much more detailed structure; and (ii) while the local compressibility profile is essentially independent of the choice of spatial discretization used to construct the profile, the spatial fluctuation profile exhibits a strong systematic dependence on the size of the subvolumes on which the profile is defined. We clarify the origin and nature of this finite-size effect.

Active crystallization from power functional theory.

We address the gas, liquid, and crystal phase behaviors of active Brownian particles in three dimensions. The nonequilibrium force balance at coexistence leads to equality of state functions for which we use power functional approximations. Motility-induced phase separation starts at a critical point and quickly becomes metastable against active freezing for Péclet numbers above a nonequilibrium triple point. The mean swim speed acts as a state variable, similar to the density of depletion agents in colloidal demixing. We obtain agreement with recent simulation results and correctly predict the strength of particle number fluctuations in active fluids.

Breakdown of Langmuir Adsorption Isotherm in Small Closed Systems.

For more than a century, monolayer adsorptions in which adsorbate molecules and adsorbing sites behave ideally have been successfully described by Langmuir's adsorption isotherm. For example, the amount of adsorbed material, as a function of concentration of the material which is not adsorbed, obeys Langmuir's equation. In this paper, we argue that this relation is valid only for macroscopic systems. However, when particle numbers of adsorbate molecules and/or adsorbing sites are small, Langmuir's model fails to describe the chemical equilibrium of the system. This is because the kinetics of forming, or the probability of observing, occupied sites arises from two-body interactions, and as such, ought to include cross-correlations between particle numbers of the adsorbate and adsorbing sites. The effect of these correlations, as reflected by deviations in predicting composition when correlations are ignored, increases with decreasing particle numbers and becomes substantial when only few adsorbate molecules, or adsorbing sites, are present in the system. In addition, any change that augments the fraction of occupied sites at equilibrium (e.g., smaller volume, lower temperature, or stronger adsorption energy) further increases the discrepancy between observed properties of small systems and those predicted by Langmuir's theory. In contrast, for large systems, these cross-correlations become negligible, and therefore when expressing properties involving two-body processes, it is possible to consider independently the concentration of each component. By applying statistical mechanics concepts, we derive a general expression of the equilibrium constant for adsorption. It is also demonstrated that in ensembles in which total numbers of particles are fixed, the magnitudes of fluctuations in particle numbers alone can predict the average chemical composition of the system. Moreover, an alternative adsorption equation, predicting the average fraction of occupied sites from the value of the equilibrium constant, is proposed. All derived relations were tested against results obtained by Monte Carlo simulations.

Fragility of the Schrödinger Cat in thermal environments

We describe the decoherence instability of Schrödinger Cat states in the two-site Bose-Hubbard model with an attractive on-site interaction between particles. For N particles with onsite attractive energy U and hopping amplitude between sites t, Cat states exist for uequiv frac{UN}{2t}<-1 at zero temperature. However, they are increasingly unstable to small thermal fluctuations as the Cat itself is increasingly well-defined and its components become well-separated. For any given u<-1, the decoherence temperature becomes smaller for large N. The loss of off-diagonal coherence peaks in the equilibrium density matrix is dominated by the thermal admixture of the first excited state of the many-body system with its ground state. Particle number fluctuations, described in the grand canonical ensemble also reduce coherence, but to a lesser degree than thermal fluctuations. The full density matrix of the Schrödinger Cat is obtained by exact numerical diagonalization of the many-body Hamiltonian and a narrow regime in the parameter space of the particle number, temperature, and U/t is identified where small Cat states may survive decoherence in a physical environment.

Stochastic analysis of chemical reactions in multi-component interacting systems at criticality

We numerically and analytically investigate the behavior of a non-equilibrium phase transition in the second Schlögl autocatalytic reaction scheme. Our model incorporates both an interaction-induced phase separation and a bifurcation in the reaction kinetics, with these critical lines coalescing at a bicritical point in the macroscopic limit. We construct a stochastic master equation for the reaction processes to account for the presence of mutual particle interactions in a thermodynamically consistent manner by imposing a generalized detailed balance condition, which leads to exponential corrections for the transition rates. In a non-spatially extended (zero-dimensional) setting, we treat the interactions in a mean-field approximation, and introduce a minimal model that encodes the physical behavior of the bicritical point and permits the exact evaluation of the anomalous scaling for the particle number fluctuations in the thermodynamic limit. We obtain that the system size scaling exponent for the particle number variance changes from at the standard non-interacting bifurcation to at the interacting bicritical point. The methodology developed here provides a generic route for the quantitative analysis of fluctuation effects in chemical reactions occurring in multi-component interacting systems.

Multimerizations, Aggregation, and Transfer Reactions of Small Numbers of Molecules.

Chemical equilibria of multimerizations in systems with small numbers of particles exhibit a behavior seemingly at odds with that observed macroscopically. In this paper, we apply the recently proposed expression of equilibrium constant for binding, which includes cross-correlations in reactants' concentrations, to write an equilibrium constant for the formation of clusters larger than two (e.g., trimer, tetramer, and pentamer) as series of two-body reactions. Results obtained by molecular dynamics simulations demonstrate that the value of this expression is constant for all concentrations and system sizes, as well as at an onset of a phase transition to an aggregated state, where densities in the system change discontinuously. In contrast, the value of the commonly utilized expression of equilibrium constant, which ignores correlations, is not constant and its variations can reach few orders of magnitude. Considering different paths for the same multimer formation, with elementary reactions of any order, yields different expressions for the equilibrium constant, yet, with exactly the same value. This is also true for routes with essentially zero probability to occur. Existence of different expressions for the same equilibrium constant imposes equalities between averages of correlated, along with uncorrelated, concentrations of participating species. Moreover, a relation between an average particle number and relative fluctuations derived for two-body reactions is found to be obeyed here as well despite couplings to additional equilibrium reactions in the system. Analyses of transfer reactions, where association and dissociation events take place on both sides of the chemical equation, further indicate the necessity to include cross-correlations in the expression of the equilibrium constant. However, in this case, the magnitudes of discrepancies of the uncorrelated expression are smaller, likely because of partial cancellation of correlations, which exist on both the reactant and product sides.

Molecular dynamics analysis of particle number fluctuations in the mixed phase of a first-order phase transition

Molecular dynamics simulations are performed for a finite non-relativistic system of particles with Lennard-Jones potential. We study the effect of liquid-gas mixed phase on particle number fluctuations in coordinate subspace. A metastable region of the mixed phase, the so-called nucleation region, is analyzed in terms of a non-interacting cluster model. Large fluctuations due to spinodal decomposition are observed. They arise due to the interplay between the size of the acceptance region and that of the liquid phase. These effects are studied with a simple geometric model. The model results for the scaled variance of particle number distribution are compared with those obtained from the direct molecular dynamic simulations.

Phase transition amplification of proton number fluctuations in nuclear collisions from a transport model approach

The time evolution of particle number fluctuations in nuclear collisions at intermediate energies ($E_{\rm lab} = 1.23-10A$ GeV) is studied by means of the UrQMD-3.5 transport model. The transport description incorporates baryonic interactions through a density-dependent potential. This allows for an implementation of a first order phase transition including a mechanically unstable region at large baryon density. The scaled variance of the baryon and proton number distributions is calculated in the central cubic spatial volume of the collisions at different times. A significant enhancement of fluctuations associated with the unstable region is observed. This enhancement persists to late times reflecting a memory effect for the fluctuations. The presence of the phase transition has a much smaller influence on the observable event-by-event fluctuations of protons in momentum space.

Particle-number fluctuations near the critical point of nuclear matter

The equation of state with quantum statistics corrections is used for particle number fluctuations $\ensuremath{\omega}$ of isotopically symmetric nuclear matter with interparticle van der Waals and Skyrme local density interactions. The fluctuations, $\ensuremath{\omega}\ensuremath{\propto}1/\mathcal{K}$, are analytically derived through the isothermal incompressibility $\mathcal{K}$ at first order over a small quantum-statistics parameter. Our approximate analytical results appear to be in good agreement with the results of accurate numerical calculations. These results are also close to those obtained by using more accurate Tolman and Rowlinson expansions of the incompressibility $\mathcal{K}$ near the critical point. A more general formula for fluctuations $\ensuremath{\omega}$, improved at the critical point, was obtained for a finite particle number average $\ensuremath{\langle}N\ensuremath{\rangle}$ by neglecting, for simplicity, small quantum statistics effects. It is shown that for a large dimensionless parameter, $\ensuremath{\alpha}\ensuremath{\propto}{\mathcal{K}}^{2}\ensuremath{\langle}N\ensuremath{\rangle}/{\mathcal{K}}^{\ensuremath{'}\ensuremath{'}}$, where ${\mathcal{K}}^{\ensuremath{'}\ensuremath{'}}$ is the second derivative of the incompressibility $\mathcal{K}$ as function of the average particle density $n$, far from the critical point $(\ensuremath{\alpha}\ensuremath{\gg}1)$, one finds the traditional asymptote, $\ensuremath{\omega}\ensuremath{\propto}1/\mathcal{K}$, for the fluctuations $\ensuremath{\omega}$. For a small parameter, $\ensuremath{\alpha}\ensuremath{\ll}1$, near the critical point, where $\mathcal{K}=0$ and $\ensuremath{\alpha}=0$, one obtains another asymptote of $\ensuremath{\omega}$. These fluctuations, having a maximum near the critical point as function of the average density $n$, for finite values of $\ensuremath{\langle}N\ensuremath{\rangle}$ are finite and relatively small, in contrast to the results of the traditional calculations.

Relation of entanglement entropy and particle number fluctuations in one-dimensional Hubbard model

Relation of entanglement entropy and particle number fluctuations in one-dimensional Hubbard model

Particle size distribution recovery from non-Gaussian intensity autocorrelation functions obtained from dynamic light scattering at ultra-low particle concentrations

Dynamic light scattering (DLS) from ultra-low concentration suspensions (the average number of particles in the scattering volume is less than ~100) gives rise to autocorrelation functions (ACFs) containing a non-Gaussian term due to particle number fluctuations. This term is difficult to characterize and account for and makes recovery of particle size distribution (PSD) information unreliable. We show that an initial analysis of the intensity ACF to determine parameters describing the amplitude and relaxation rate of the non-Gaussian term and then using these parameters to create a better theoretical non-Gaussian ACF model allows a more accurate recovery of the PSD. The modified model is consistent with the measured ACF data, and a reconstructed kernel matrix matching the measured data is obtained. When compared with the usual kernel function reconstruction (KFR) method, the proposed method gives significantly improved PSD recovery accuracy with experimental data. Furthermore, the PSDs obtained have no obvious differences to those obtained from measurements at normal particle concentrations. • Fitting the measured ACF data with a non-Gaussian ACF model of lower concentration. • Reducing focused beam waist value to obtain non-Gaussian model at lower concentration. • Providing a solution for nanoparticle size measurement at ultra-low concentration.

Escaping many-body localization in an exact eigenstate

Isolated quantum systems typically follow the eigenstate thermalization hypothesis, but there are exceptions, such as many-body localized (MBL) systems and quantum many-body scars. Here, we present the study of a weak violation of MBL due to a special state embedded in a spectrum of MBL states. The special state is not MBL since it displays logarithmic scaling of the entanglement entropy and of the bipartite fluctuations of particle number with subsystem size. In contrast, the bulk of the spectrum becomes MBL as disorder is introduced. We establish this by studying the entropy as a function of disorder strength and by observing that the level spacing statistics undergoes a transition from Wigner-Dyson to Poisson statistics as the disorder strength is increased.

Entanglement entropy of the quantum Hall edge and its geometric contribution

Generally speaking, entanglement entropy (EE) between two subregions of a gapped quantum many-body state is proportional to the area/length of their interface due to the short-range quantum correlation. However, the so-called area law is violated logarithmically in a quantum critical phase. Moreover, the subleading correction exists in long-range entangled topological phases. It is referred to as topological EE which is related to the quantum dimension of the collective excitation in the bulk. Furthermore, if a non-smooth sharp angle is in the presence of the subsystem boundary, a universal angle dependent geometric contribution is expected to appear in the subleading correction. In this work, we simultaneously explore the geometric and edge contributions in the integer quantum Hall (IQH) state and its edge reconstruction in a unified bipartite method. Their scaling is found to be consistent with conformal field theory (CFT) predictions and recent results of particle number fluctuation calculations.

Van der waals equation of state

Van der Waals (vdW) invented his equation of state about 150 year ago. This equation described the liquidgas phase transition and predicted an existence of the critical point. The vdW equation of state remains today the most familiar and one of the most successful model in molecular physics. It is presented in all text books on statistical physics. However, several important questions concerning the vdW model had no answers. Only very recently these questions were discussed in the literature, and several important extensions of the vdW equation of state were developed. These new results presented in this article correspond to the grand canonical ensemble formulation, the effects of quantum statistics, and applications of the vdW model to nuclear matter taking into account Fermi statistics for interacting protons and neutrons. A special attention is also paid to the particle number fluctuations in a vicinity of the vdW critical point.

Kirkwood-Buff integrals: From fluctuations in finite volumes to the thermodynamic limit.

The Kirkwood-Buff theory is a cornerstone of the statistical mechanics of liquids and solutions. It relates volume integrals over the radial distribution function, so-called Kirkwood-Buff integrals (KBIs), to particle number fluctuations and thereby to various macroscopic thermodynamic quantities such as the isothermal compressibility and partial molar volumes. Recently, the field has seen a strong revival with breakthroughs in the numerical computation of KBIs and applications to complex systems such as bio-molecules. One of the main emergent results is the possibility to use the finite volume KBIs as a tool to access finite volume thermodynamic quantities. The purpose of this Perspective is to shed new light on the latest developments and discuss future avenues.

Partial molar properties from single molecular dynamics simulations

ABSTRACT In this manuscript, we show how to compute partial molar properties (e.g. partial molar volumes, energies, and enthalpies) of fluid mixtures from single Molecular Dynamics simulations in the microcanonical or canonical ensemble, using only relatively simple post-processing of trajectories. The method uses least squares linear regression of local fluctuations of particle numbers and energies in combination with the Small System Method, and is in principle valid for any number of components and for any type of intermolecular interactions. For multicomponent systems, only a single simulation is needed for a given composition of the mixture. Simulations of a binary WCA mixture are used to illustrate the method, and to investigate the effect of system size.

Critical point particle number fluctuations from molecular dynamics

We study fluctuations of particle number in the presence of critical point by utilizing molecular dynamics simulations of the classical Lennard-Jones fluid in a periodic box. The numerical solution of the $N$-body problem naturally incorporates all correlations, exact conservation laws, and finite size effects, allowing us to study the fluctuation signatures of the critical point in a dynamical setup. We find that large fluctuations associated with the critical point are observed when measurements are performed in coordinate subspace, but, in the absence of collective flow and expansion, are essentially washed out when momentum cuts are imposed instead. We put our findings in the context of event-by-event fluctuations in heavy-ion collisions.

Projected BCS theory for the unification of antiferromagnetism and strongly correlated superconductivity

A close connection between antiferromagnetism and superconductivity is at the core of high-temperature superconductivity. Here, we put forward the projected BCS theory for the unification of antiferromagnetism and strongly correlated superconductivity. Specifically, it is shown that, with the $d$-wave pairing symmetry, the projected BCS theory can provide excellent trial states at general doping for the exact ground states of the $t\text{\ensuremath{-}}J$ model in the square lattice, generating a unified theory of high-temperature superconductivity as a continuous function of hole concentration. A key to the success of the projected BCS theory is an accurate treatment of the strong correlation between Cooper pairs, which not only causes the breakdown of superconductivity itself at half filling but also defines the precise nature of strongly correlated superconductivity at moderate doping. Also, via the proper incorporation of particle number fluctuations, the projected BCS theory allows direct computation of the superconducting order parameter, shedding important light on the pseudogap phenomenon.