Statistical Mechanics Of Fluids Research Articles

Statistical physics of active matter, cell division and cell aggregation

In these Lecture Notes we aim at clarifying how soft matter physics, and herein notably statistical mechanics and fluid mechanics, can be engaged to understand and manipulate non-equilibrium systems consisting of numerous (microscopic) constituents that convert (chemical) energy to mechanical energy, or vice versa, and that are known as active matter. Hydrodynamic theory, vitally extended to include (anisotropic) active stress, provides an astonishingly successful scaffold for tackling the problem of spontaneous flow in active nematics, all the way to active turbulence. The laws of physics, nonchalantly trespassing the border crossing between inanimate particle and living cell, are seen to perform cum laude in describing the bi-directional coupling between division and apoptosis on the one hand and mechanical stress on the other. Fluidization of cellular tissue by cell division is a conceptual leap in this arena. The active behavior of nematic tissues (cell extrusion, multilayer formation, …) turns out to be controlled by topological defects in the orientational order. Playgrounds by excellence for exhibiting stress-growth coupling are multicellular spheroids serving as model tumors, and cysts used as stem cell factories for cell therapy. Finally, our study of villi and crypts in the intestine furnishes a synthesis of various concepts explored. Cell mechanical pressure and cell layer geometrical curvature turn out to provide the dynamical ingredients which, when coupled to the cell division rate, allow one to develop a physical theory of tissue morphology which hopefully will have practical impact on cancer research.

Statistical fluid mechanics: Dynamics equations and linear response theory

The statistical nature of discrete fluid molecules with random thermal motion so far has not been considered in mainstream fluid mechanics based on Navier–Stokes equations, wherein fluids have been treated as a continuum breaking into many macroscopically infinitely small (but microscopically large enough) mass elements with their motion only characterized by center-of-mass velocity. Here, we provide a Statistical Mechanical approach to address fluid dynamics by considering statistical velocity distribution of discrete molecules within macroscopically infinitely small volume elements as well as their center-of-mass velocity. Dynamics equations governing the evolution of physical variables have been proposed, Green's functions have been obtained, and the linear response theory has been applied to study physical situations with external heat perturbation. It is found that the propagation of heat, center-of-mass motion, and sound are intrinsically integrated in Statistical fluid dynamics. This work lays down the foundation for applications of Statistical fluid mechanics.

Remarks on the principles of statistical fluid mechanics.

This is an idiosyncratic survey of statistical fluid mechanics centering on the Hopf functional differential equation. Using the Burgers equation for illustration, we review several functional integration approaches to the theory of turbulence. We note in particular that some important contributions have been brought about by researchers working on wave propagation in random media, among which Uriel Frisch is not an exception. We also discuss a particular finite-dimensional approximation for the Burgers equation. This article is part of the theme issue ''Scaling the turbulence edifice (part 1)'.

Validity of the compressibility equation and Kirkwood-Buff theory for crystalline matter.

Volume integrals over the radial pair-distribution function, so-called Kirkwood-Buff integrals (KBIs), play a central role in the theory of solutions by linking structural with thermodynamic information. The simplest example is the compressibility equation, a fundamental relation in statistical mechanics of fluids. Until now, KBI theory could not be applied to crystals because the integrals strongly diverge when computed in the standard way. We solve the divergence problem and generalize KBI theory to crystalline matter by using the recently proposed finite-volume theory. For crystals with harmonic interaction, we derive an analytic expression for the peak shape of the pair-distribution function at finite temperature. From this we demonstrate that the compressibility equation holds exactly in harmonic crystals.

Temperature profiles, plumes, and spectra in the surface layer of convective boundary layers

We survey temperature patterns and heat transport in convective atmospheric boundary layers (CBLs). We use the word “plumes” to describe the emergent temperature patterns, in much the same way that “eddies” describe patterns of motion in turbulent flows. We introduce a two-temperature (2T) toy model to connect the cross-sectional areas of plumes to the scaling properties of temperature gradients, temperature spectra, and heat transport. We find that the half power law (z−1/2, where z is the height above the surface) form of the temperature profile reflects the change in plume cross-sectional area with height and that this is consistent with the mixed length scale required to collapse the peak regions of temperature spectra above the surface friction layer (SFL). We introduce new scaling results for temperature spectra and heat flux cospectra that extend this relationship to most of the SFLs. The spectral properties change in the bottom tenth of the SFL, where the temperature profile becomes logarithmic and temperature fluctuations increasingly display Gaussian statistics. At such small heights, the self-similarity property of the plumes reflects their randomness rather than self-similarity in the order observed above. We conclude with a general discussion, contrasting our interpretation of the role of buoyancy, as being associated with the largest structures in CBL flows, with that of Richardson [Proc. R. Soc. A 87, 354–373 (1920)], who neglected large structures and assumed that it acts locally, on the small eddies. Richardson’s ideas still inform the currently accepted, statistical fluid mechanics model of boundary-layer flows.

The vicinity of an equilibrium three-phase contact line using density-functional theory: density profiles normal to the fluid interface

ABSTRACTThe paper by Nold et al. [Phys. Fluids 26 (7), 072001 (2014)] examined density profiles and the micro-scale structure of an equilibrium three-phase (liquid–vapour–solid) contact line in the immediate vicinity of the wall using elements from the statistical mechanics of classical fluids, namely density-functional theory. The present research note, building on the above work, further contributes to our understanding of the nanoscale structure of a contact line by quantifying the strong dependence of the liquid–vapour density profile on the normal distance to the interface, when compared to the dependence on the vertical distance to the substrate. A recent study by Benet et al. [J. Phys. Chem. C 118 (38), 22079 (2014)] has shown that this could explain the emergence of a film-height-dependent surface tension close to the wall, with implications for the Frumkin–Derjaguin theory.

A diagrammatic analysis of the variational perturbation method for classical fluids.

The statistical mechanics of classical fluids can be approached from the particle perspective, where the focus is on the various positions and interactions of the particles, and from the field perspective, where the focus is on the form of the interaction fields generated by the particles. In this work, we combine these two perspectives by examining the variational perturbation method for classical fluids, which has been widely used to describe nonuniform electrolyte systems. Most of this work has been for low orders of the approximation, it has been limited to cases where the electrostatic interactions are weak. We present an exact diagrammatic representation of the method, which greatly facilitates the enumeration and evaluation of higher order corrections to the free energy functional. This framework is able to encapsulate several different approximate theories. Performing a cumulant expansion, leads to the Debye-Hückel and higher order corrections. Including the contribution of chain diagrams leads to a theory closely related to the splitting theory [Hatlo and Lue, Europhys. Lett., 2010, 89, 25002], which has been shown to be accurate from the weak through to the strong coupling limits. Including all chain and ring diagrams leads to the hypernetted chain approximation; this is a more direct route to the conventional derivation, which also requires a renormalization of the Mayer f-bonds to the total correlation functions. These approximations to the variational perturbation method are applied to the classical one-component plasma in order to assess their relative accuracy and understand their relationship to each other. Strategies for developing improved approximations are discussed.

10th Biennial Conference on Classical and Quantum Relativistic Dynamics of Particles and Fields

10th Biennial Conference on Classical and Quantum Relativistic Dynamics of Particles and Fields

Effects of smooth random surface on fluid monolayer thermodynamics

We consider the lattice gas approach to statistical mechanics of fluid adsorbed on random surfaces with fluid-fluid and fluid-surface potentials. It was shown that effective Hamiltonian contains quenched random interactions and random site fields. Their statistical features combine the properties of random geometry and fluid-fluid pair interaction potential. The high-temperature expansion leads to infinite-ranged random field model and Sherrington–Kirkpatrick spin-glass model. Thermodynamic properties are evaluated using replica theory procedure widely used to analyze quenched disorder systems. On the other hand we consider the random field model in random graph with finite connectivity instead of previous “infinite-ranged” approximations. This model has been investigated using finite connectivity technique. The replica symmetry ansatz for the order function is expressed in terms of an effective-field distribution. Analysis of random geometry effects on thermodynamic properties in such approach was done for the first time.

Uniform quantized electron gas

In this work we study the correlation energy of the quantized electron gas of uniform density at temperature T = 0. To do so we utilize methods from classical statistical mechanics. The basis for this is the Feynman path integral for the partition function of quantized systems. With this representation the quantum mechanical problem can be interpreted as, and is equivalent to, a classical polymer problem in four dimensions where the fourth dimension is imaginary time. Thus methods, results, and properties obtained in the statistical mechanics of classical fluids can be utilized. From this viewpoint we recover the well known RPA (random phase approximation). Then to improve it we modify the RPA by requiring the corresponding correlation function to be such that electrons with equal spins can not be on the same position. Numerical evaluations are compared with well known results of a standard parameterization of Monte Carlo correlation energies.

John Leask Lumley

John Leask Lumley

Introduction to Classical Density Functional Theory by a Computational Experiment

We propose an in-silico experiment to introduce classical density functional theory (cDFT). Den- sity functional theories, whether quantum or classical, rely on abstract concepts that are non- intuitive. However, they are at the heart of powerful tools and active fields of research in both physics and chemistry. They led to the 1998 Nobel Prize in chemistry. DFT is illustrated here in its most simple and yet physically relevant form: the classical density functional theory of an ideal fluid of classical particles. For illustration purpose, it is applied to the prediction of the molecular structure of liquid neon. The numerical experiment proposed therein is built around the writing of a cDFT code by students in Mathematica. Students thus have to deal with (i) the cDFT theory, (ii) some basic concepts of statistical mechanics of simple fluids, (iii) functional minimization, and (iv) a useful functional programming language. This computational experiment is proposed during a molecular simulation class, but may also be of interest in a quantum chemistry class to illustrate electronic DFT, if one highlights the analogies between the quantum and classical DFTs.

Computation of pair distribution functions and three-dimensional densities with a reduced variance principle

No fancy statistical objects here, we go back to the computation of one of the most basic and fundamental quantities in the statistical mechanics of fluids, namely the pair distribution functions. Those functions are usually computed in molecular simulations by using histogram techniques. We show here that they can be estimated using a global information on the instantaneous forces acting on the particles, and that this leads to a reduced variance compared to the standard histogram estimators. The technique is extended successfully to the computation of three-dimensional solvent densities around tagged molecular solutes, quantities that are noisy and very long to converge, using histograms.

Local order variations in confined hard-sphere fluids

Pair distributions of fluids confined between two surfaces at close distance are of fundamental importance for a variety of physical, chemical, and biological phenomena, such as interactions between macromolecules in solution, surface forces, and diffusion in narrow pores. However, in contrast to bulk fluids, properties of inhomogeneous fluids are seldom studied at the pair-distribution level. Motivated by recent experimental advances in determining anisotropic structure factors of confined fluids, we analyze theoretically the underlying anisotropic pair distributions of the archetypical hard-sphere fluid confined between two parallel hard surfaces using first-principles statistical mechanics of inhomogeneous fluids. For this purpose, we introduce an experimentally accessible ensemble-averaged local density correlation function and study its behavior as a function of confining slit width. Upon increasing the distance between the confining surfaces, we observe an alternating sequence of strongly anisotropic versus more isotropic local order. The latter is due to packing frustration of the spherical particles. This observation highlights the importance of studying inhomogeneous fluids at the pair-distribution level.

Perspective: Coulomb fluids—Weak coupling, strong coupling, in between and beyond

We present a personal view on the current state of statistical mechanics of Coulomb fluids with special emphasis on the interactions between macromolecular surfaces, concentrating on the weak and the strong coupling limits. Both are introduced for a (primitive) counterion-only system in the presence of macroscopic, uniformly charged boundaries, where they can be derived systematically. Later we show how this formalism can be generalized to the cases with additional characteristic length scales that introduce new coupling parameters into the problem. These cases most notably include asymmetric ionic mixtures with mono- and multivalent ions that couple differently to charged surfaces, ions with internal charge (multipolar) structure and finite static polarizability, where weak and strong coupling limits can be constructed by analogy with the counterion-only case and lead to important new insights into their properties that cannot be derived by any other means.

Statistical behavior of the orthogonal subgrid scale stabilization terms in the finite element large eddy simulation of turbulent flows

Numerical simulations have proved that Variational Multiscale Methods (VMM) perform well as pure numerical large eddy simulation (LES) models. In this paper we focus on the orthogonal subgrid scale (OSS) finite element method and make an analysis of the statistical behavior of its stabilization terms in the quasi static approximation. This is done by resorting to results from classical statistical fluid mechanics concerning two point velocity, pressure and combined correlation functions of various orders. Given a fine enough mesh with characteristic element size h in the inertial subrange of a turbulent flow, it is shown that the rate of transfer of subgrid kinetic energy provided by the OSS stabilization terms does not depend on h and that it equals the molecular physical dissipation rate (up to a dimensionless constant that only depends on the finite element shapes) for a proper redesign of the standard parameters of the formulation. This is a noteworthy fact taking into account that the subgrid stabilization terms do not arise from physical considerations, but from the mathematical necessity to allow equal interpolation for the pressure and velocity fields, as well as to control convection. Therefore, the obtained results contribute somehow to the line of reasoning supporting that pure numerical approaches (i.e., without introducing additional physical models) could probably suffice in the LES simulation of turbulent flows.

Thermodynamic scaling and corresponding states for the self-diffusion coefficient of non-conformal soft-sphere fluids

In this work, we explore transport properties of a special type of repulsive spheres that exhibit remarkable scaling of their thermodynamic properties. In order to accomplish that we propose a new way to derive and express effective hard-sphere diameters for transport properties of simple fluids. The procedure relies on mapping the system's transport properties, in the low density limit, to the hard-sphere fluid. We have chosen a set of soft-sphere systems characterised by a well-defined variation of their softness. These systems represent an extension of the repulsive Lennard-Jones potential widely used in statistical mechanics of fluids and are an accurate representation of the effective repulsive potentials of real systems. The self-diffusion coefficient of the soft-sphere fluids is obtained by equilibrium molecular dynamics. The soft-sphere collision integrals of different systems are shown to follow quite simple relationships between each other. These collision integrals are incorporated, through the definition of the effective hard-sphere diameter, in the resulting equation for the self-diffusion coefficient. The approach followed exhibits a density rescaling that leads to a single master curve for all systems and temperatures. The scaling is carried through to the level of the mean-squared displacement.

Thermodynamic properties of non-conformal soft-sphere fluids with effective hard-sphere diameters

In this work we study a set of soft-sphere systems characterised by a well-defined variation of their softness. These systems represent an extension of the repulsive Lennard-Jones potential widely used in statistical mechanics of fluids. This type of soft spheres is of interest because they represent quite accurately the effective intermolecular repulsion in fluid substances and also because they exhibit interesting properties. The thermodynamics of the soft-sphere fluids is obtained via an effective hard-sphere diameter approach that leads to a compact and accurate equation of state. The virial coefficients of soft spheres are shown to follow quite simple relationships that are incorporated into the equation of state. The approach followed exhibits the rescaling of the density that produces a unique equation for all systems and temperatures. The scaling is carried through to the level of the structure of the fluids.

Statistical Fluid Mechanics and Statistical Mechanics of Fluid Turbulence

Turbulence in a fluid has two mutually contradictory aspects, that is, the apparent ran-domeness as a whole and the intrinsic determinicity due to the fluid-dynamical equations. In the traditional approarch to this subject, the velocity field of turbulence has been represented by the mean products of the turbulent velocities at several points and a time, and the equations governing the dynamical system composed of the mean velocity products are solved to obtain the mean velocity products as the deterministic functions in time. The works along this approach constitute the main body of turbulence research as outlined by Monin and Yaglom (1975) under the title of 'Statistical Fluid Mechanics'. It should be noted, however, that this approach has the diffculty of unclosedness of the equations for the mean velocity products due to the nonlinearity of the Navier-Stokes equations and an appropriate closure hypothesis is still awaited.In the statistical approach to turbulence, on the other hand, the random velocity field of turbulence is represented by the joint-probability distributions of the multi-point turbulent velocities. This approach has been taken by Lundgren (1967) and Monin (1967) independently, and the system of equations for the probability distributions of the multi-point velocities has been formulated. This system of equations is also unclosed, but in this case the problem is much easier to deal with since the unclosedness is not due to the nonlinearity but to the higher-order derivatives in the viscous term of the Navier-Stokes equations. Tatsumi (2001) proposed the cross-independence closure hypothesis for this purpose and proved its validity for homogeneous isotropic turbulence. More recently, the theory has extended by Tatsumi (2011) to general inhomogeneous turbulence and the closure is shown to provide an exact closure. This theory is outlined and discussed in the later part of this paper.

Electron effective mass in the strongly correlated two-dimensional uniform electron fluid from finite-temperature calculations

The very-low temperature thermal effective mass m* of paramagnetic and ferromagnetic electrons in a uniform electron fluid in two dimensions is studied. Analytical and numerical evaluations are used to meaningfully define an m*, even in the the Hartree-Fock approximation. The Hartree-Fock m* decreases linearly with the electron-disk radius r_s. Correlation effects lead to strong cancellations between exchange and correlation. Thus the effective mass is enhanced with increasing r_s for the unpolarized fluid, while m* decreases with the r_s of the polarized fluid. The effective mass is calculated from the coefficient of the quadratic temperature dependence of exchange-correlation free energy F_{xc}. This is calculated in a physically transparent manner using a new formula for the effective mass. This uses the T=0 pair-distribution functions of Gori-Giorgi et al., and the temperature derivative of a quantum analogue of the potential of mean-force well known in the statistical mechanics of classical fluids. The results are compared with recent quantum Monte-Carlo simulations at T=0, as well as with other available experimental and theoretical data for the effective mass.