System Size Dependence of the Diffusion Coefficients in MD Simulations: A Simple Correction Formula for Pure Dense Fluids.

A practical correction formula relating the self-diffusion coefficient of dense liquids from molecular dynamics (MD) simulations with periodic boundary conditions to the self-diffusion coefficient in the thermodynamic limit is discussed. This formula applies to pure dense fluids and has a very simple form D = D0(1 - γN-1/3), where D0 is the self-diffusion coefficient in the thermodynamic limit and N is the number of particles in the simulation. The numerical factor γ is dependent on the geometry of the simulation cell. Remarkably, γ ≃ 1.0 is the most popular cubic geometry. The success of this formula is supported by results from MD simulations, including very recent simulations with a "magic" simulation geometry.

Diffusion mobility increases linearly on liquid binodals above triple point.

Self-diffusion in fluids has been thoroughly studied numerically, but even for simple liquids just a few scaling relationships are known. Relations between diffusion, excitation spectra, and character of the interparticle interactions remain poorly understood. Here, we show that diffusion mobility of particles in simple fluids increases linearly on the liquid branch of the liquid-gas binodal, from the triple point almost up to the critical point. With molecular dynamics simulations, we considered bulk systems of particles interacting via a generalised Lennard-Jones potential, as well as ethane. Using a two-oscillator model for the analysis of excitations, we observed that the mobility (inverse diffusion) coefficient on the liquid-gas binodal increases linearly above the triple point until the dispersion of high-frequency spectra has a solid-like (oscillating) shape. In terms of a separate mode analysis (of longitudinal and transverse modes), this corresponds to crossed modes in the intermediate range of wavenumbers q, between the hydrodynamic regime (small q) and the regime of individual particle motion (large q). The results should be interesting for a broad community in physics and chemistry of fluids, since self-diffusion is among the most fundamental transport phenomena, important for prospective chemical technologies, micro-, nanofluidics, and biotechnologies.

Self-Diffusion in Simple Liquids as a Random Walk Process.

It is demonstrated that self-diffusion in dense liquids can be considered a random walk process; its characteristic length and time scales are identified. This represents an alternative to the often assumed hopping mechanism of diffusion in the liquid state. The approach is illustrated using the one-component plasma model.

Entropy of simple fluids with repulsive interactions near freezing.

Among different thermodynamic properties of liquids, the entropy is one of the hardest quantities to estimate. Therefore, the development of models allowing accurate estimations of the entropy for different mechanisms of interatomic interactions represents an important problem. Here, we propose a method for estimating the excess entropy of simple liquids not too far from the liquid-solid phase transition. The method represents a variant of cell theory, which particularly emphasizes relations between liquid state thermodynamics and collective modes properties. The method is applied to calculate the excess entropy of inverse-power-law fluids with ∝r-n repulsive interactions. The covered range of potential softness is extremely wide, including the very soft Coulomb (n = 1) case, much steeper n = 6 and n = 12 cases, and the opposite hard-sphere interaction limit (n = ∞). An overall reasonably good agreement between the method's outcome and existing "exact" results is documented at sufficiently high fluid densities. Its applicability condition can be conveniently formulated in terms of the excess entropy itself. The method is also applied to the Lennard-Jones potential but demonstrates considerably lower accuracy in this case. Our results should be relevant to a broad range of liquid systems that can be described with isotropic repulsive interactions, including liquid metals, macromolecular systems, globular proteins, and colloidal suspensions.

Vibrational model of thermal conduction for fluids with soft interactions.

A vibrational model of heat transfer in simple liquids with soft pairwise interatomic interactions is discussed. A general expression is derived, which involves an averaging over the liquid collective mode excitation spectrum. The model is applied to quantify heat transfer in a dense Lennard-Jones liquid and a strongly coupled one-component plasma. Remarkable agreement with the available numerical results is documented. A similar picture does not apply to the momentum transfer and shear viscosity of liquids.

Sound Velocities of Lennard-Jones Systems Near the Liquid-Solid Phase Transition.

Longitudinal and transverse sound velocities of Lennard-Jones systems are calculated at the liquid-solid coexistence using the additivity principle. The results are shown to agree well with the "exact" values obtained from their relations to excess energy and pressure. Some consequences, in particular in the context of the Lindemann's melting rule and Stokes-Einstein relation between the self-diffusion and viscosity coefficients, are discussed. Comparison with available experimental data on the sound velocities of solid argon at melting conditions is provided.

Reduction of the Coulomb logarithm due to electron-neutral collisions.

The frictional force (stopping power) acting on a test electron moving through an ideal electron gas is calculated by taking into account electron-neutral atom collisions using the linear plasma response formalism. This allows us to elucidate how the effective Coulomb logarithm is affected by electron-neutral collisions. In agreement with a recent investigation by Hagelaar, Donko, and Dyatko [Phys. Rev. Lett. 123, 025004 (2019)PRLTAO0031-900710.1103/PhysRevLett.123.025004], we observe that the effective Coulomb logarithm decreases considerably due to electron-neutral collisions and becomes inversely proportional to the collision frequency in the highly collisional limit.

Comment on "Shear modulus of two-dimensional Yukawa or dusty-plasma solids obtained from the viscoelasticity in the liquid state".

In a recent paper [Wang, Huang, and Feng, Phys. Rev. E 99, 063206 (2019)2470-004510.1103/PhysRevE.99.063206], Langevin dynamical simulation results related to the shear modulus G of a two-dimensional liquid dusty plasma were reported. The purpose of this Comment is to provide a comparison with available theoretical models to calculate G and to indicate the correct way of interpreting the numerical results.

Onset of transverse (shear) waves in strongly-coupled Yukawa fluids.

A simple practical approach to describe transverse (shear) waves in strongly-coupled Yukawa fluids is presented. Theoretical dispersion curves, based on hydrodynamic consideration, are shown to compare favorably with existing numerical results for plasma-related systems in the long-wavelength regime. The existence of a minimum wave number below which shear waves cannot propagate and its magnitude are properly accounted in the approach. The relevance of the approach beyond plasma-related Yukawa fluids is demonstrated by using experimental data on transverse excitations in liquid metals Fe, Cu, and Zn, obtained from inelastic x-ray scattering. Some potentially important relations, scalings, and quasi-universalities are discussed. The results should be interesting for a broad community in chemical physics, materials physics, physics of fluids and glassy state, complex (dusty) plasmas, and soft matter.

Collective modes of two-dimensional classical Coulomb fluids.

Molecular dynamics simulations have been performed to investigate in detail collective modes spectra of two-dimensional Coulomb fluids in a wide range of coupling. The obtained dispersion relations are compared with theoretical approaches based on quasi-crystalline approximation, also known as the quasi-localized charge approximation, in the plasma-related context. An overall satisfactory agreement between theory and simulations is documented for the longitudinal mode at moderate coupling and in the long-wavelength domain at strong coupling. For the transverse mode, satisfactory agreement in the long-wavelength domain is only reached at very strong coupling, when the cutoff wave-number below which shear waves cannot propagate becomes small. The dependence of the cutoff wave-number for shear waves on the coupling parameter is obtained.

Thermodynamics and dynamics of two-dimensional systems with dipolelike repulsive interactions.

Thermodynamics and dynamics of a classical two-dimensional system with dipolelike isotropic repulsive interactions are studied systematically using extensive molecular dynamics (MD) simulations supplemented by appropriate theoretical approximations. This interaction potential, which decays as an inverse cube of the interparticle distance, belongs to the class of very soft long-ranged interactions. As a result, the investigated system exhibits certain universal properties that are also shared by other related soft-interacting particle systems (like, for instance, the one-component plasma and weakly screened Coulomb systems). These universalities are explored in this article to construct a simple and reliable description of the system thermodynamics. In particular, Helmholtz free energies of the fluid and solid phases are derived, from which the location of the fluid-solid coexistence is determined. The quasicrystalline approximation is applied to the description of collective modes in dipole fluids. Its simplification, previously validated on strongly coupled plasma fluids, is used to derive explicit analytic dispersion relations for the longitudinal and transverse wave modes, which compare satisfactory with those obtained from direct MD simulations in the long-wavelength regime. Sound velocities of the dipole fluids and solids are derived and analyzed.

Thermodynamics of two-dimensional Yukawa systems across coupling regimes.

Thermodynamics of two-dimensional Yukawa (screened Coulomb or Debye-Hückel) systems is studied systematically using molecular dynamics (MD) simulations. Simulations cover very broad parameter range spanning from weakly coupled gaseous states to strongly coupled fluid and crystalline states. Important thermodynamic quantities, such as internal energy and pressure, are obtained and accurate physically motivated fits are proposed. This allows us to put forward simple practical expressions to describe thermodynamic properties of two-dimensional Yukawa systems. For crystals, in addition to numerical simulations, the recently developed shortest-graph interpolation method is applied to describe pair correlations and hence thermodynamic properties. It is shown that the finite-temperature effects can be accounted for by using simple correction of peaks in the pair correlation function. The corresponding correction coefficients are evaluated using MD simulation. The relevance of the obtained results in the context of colloidal systems, complex (dusty) plasmas, and ions absorbed to interfaces in electrolytes is pointed out.

Note: Sound velocity of a soft sphere model near the fluid-solid phase transition.

The quasilocalized charge approximation is applied to estimate the sound velocity of simple soft sphere fluid with the repulsive inverse-power-law interaction. The obtained results are discussed in the context of the sound velocity of the hard-sphere system and of liquid metals at the melting temperature.

Practical thermodynamics of Yukawa systems at strong coupling.

Simple practical approach to estimate thermodynamic properties of strongly coupled Yukawa systems, in both fluid and solid phases, is presented. The accuracy of the approach is tested by extensive comparison with direct computer simulation results (for fluids and solids) and the recently proposed shortest-graph method (for solids). Possible applications to other systems of softly repulsive particles are briefly discussed.

Fluid approach to evaluate sound velocity in Yukawa systems and complex plasmas.

The conventional fluid description of multicomponent plasma, supplemented by an appropriate equation of state for the macroparticle component, is used to evaluate the longitudinal sound velocity of Yukawa fluids. The obtained results are in very good agreement with those obtained earlier employing the quasilocalized charge approximation and molecular dynamics simulations in a rather broad parameter regime. Thus, a simple yet accurate tool to estimate the sound velocity across coupling regimes is proposed, which can be particularly helpful in estimating the dust-acoustic velocity in strongly coupled dusty (complex) plasmas. It is shown that, within the present approach, the sound velocity is completely determined by particle-particle correlations and the neutralizing medium (plasma), apart from providing screening of the Coulomb interaction, has no other effect on the sound propagation. The ratio of the actual sound velocity to its "ideal gas" (weak coupling) scale only weakly depends on the coupling strength in the fluid regime but exhibits a pronounced decrease with the increase of the screening strength. The limitations of the present approach in applications to real complex plasmas are briefly discussed.

Practical expressions for the internal energy and pressure of Yukawa fluids.

Simple practical expressions that allow estimation of thermodynamic properties of Yukawa fluids in a wide range of coupling, up to the fluid-solid phase transition, are presented. These expressions demonstrate excellent agreement with the available results from numerical simulations. The approach provides simple and accurate tools to estimate thermodynamic properties of Yukawa fluids and related systems in a broad range of parameters.

Communication: Universality of the melting curves for a wide range of interaction potentials.

We demonstrate that the melting curves of various model systems of interacting particles collapse to (or are located very close to) a universal master curve on a plane of appropriately chosen scaled variables. The physics behind this universality is discussed. An equation for the emerging "universal melting curve" is proposed. The obtained results can be used to approximately predict melting of various substances in a wide range of conditions.

Accurate freezing and melting equations for the Lennard-Jones system.

Analyzing three approximate methods to locate liquid-solid coexistence in simple systems, an observation is made that all of them predict the same functional dependence of the temperature on density at freezing and melting of the conventional Lennard-Jones (LJ) system. The emerging equations can be written as T=Aρ(4)+Bρ(2) in normalized units. We suggest to determine the values of the coefficients A at freezing and melting from the high-temperature limit, governed by the inverse 12th power repulsive potential. The coefficients B can be determined from the triple point parameters of the LJ fluid. This produces freezing and melting equations which are exact in the high-temperature limit and at the triple point and show remarkably good agreement with numerical simulation data in the intermediate region.

Freezing of Lennard-Jones-type fluids.

We put forward an approximate method to locate the fluid-solid (freezing) phase transition in systems of classical particles interacting via a wide range of Lennard-Jones-type potentials. This method is based on the constancy of the properly normalized second derivative of the interaction potential (freezing indicator) along the freezing curve. As demonstrated recently it yields remarkably good agreement with previous numerical simulation studies of the conventional 12-6 Lennard-Jones (LJ) fluid [S.A.Khrapak, M.Chaudhuri, G.E.Morfill, Phys. Rev. B 134, 052101 (2010)]. In this paper, we test this approach using a wide range of the LJ-type potentials, including LJ n-6 and exp-6 models, and find that it remains sufficiently accurate and reliable in reproducing the corresponding freezing curves, down to the triple-point temperatures. One of the possible application of the method--estimation of the freezing conditions in complex (dusty) plasmas with "tunable" interactions--is briefly discussed.

Momentum transfer in complex plasmas.

Momentum transfer in complex plasmas (systems consisting of ions, electrons, neutrals, and charged macroscopic grains) is investigated assuming an interaction potential between the charged species of the screened Coulomb (Yukawa) type. Momentum transfer cross sections and rates are derived. Applications of the results are discussed; in particular, we classify the possible states of complex plasmas in terms of the momentum transfer due to grain-grain collisions and its competition with that due to interaction with the surrounding medium. The resulting phase diagrams are presented.