Frenkel Line Research Articles

Molecular dynamics analysis of the crossover phenomenon in supercritical carbon dioxide

Supercritical carbon dioxide (SCO2) finds widespread applications but its complex phase behavior near and beyond the critical point remains unclear. In this work, extensive focus has been invested in the thermodynamic transitions of SCO2 from a microscopic perspective. It is revealed that both the radial distribution function and structure factor exhibit apparent crossover phenomena as temperature changes. Remarkably, our findings demonstrate an unprecedented agreement between the predicted crossover points using different functions and the experimental Frenkel Line (FL), with a deviation of merely 5.6%. By applying the same method, the FL crossover region is successfully predicted and extended up to an impressive pressure of 200 MPa. Notably, this prediction is a valuable guide in narrowing down the temperature range for further experimental tests. Concurrently, a correlation between the coordination number and the FL is discovered. Overall, our research provides compelling evidence supporting the FL as thermodynamic transitions between the gas-like and liquid-like regions and presents a novel and reliable approach for identifying the FL, which offers valuable theoretical insights into the phase behavior in the supercritical state.

Entropy of strongly coupled Yukawa fluids.

The entropy of strongly coupled Yukawa fluids is discussed from several perspectives. First, it is demonstrated that a vibrational paradigm of atomic dynamics in dense fluids can be used to obtain a simple and accurate estimate of the entropy without any adjustable parameters. Second, it is explained why a quasiuniversal value of the excess entropy of simple fluids at the freezing point should be expected, and it is demonstrated that a remaining very weak dependence of the freezing point entropy on the screening parameter in the Yukawa fluid can be described by a simple linear function. Third, a scaling of the excess entropy with the freezing temperature is examined, a modified form of the Rosenfeld-Tarazona scaling is put forward, and some consequences are briefly discussed. Fourth, the location of the Frenkel line on the phase diagram of Yukawa systems is discussed in terms of the excess entropy and compared with some predictions made in the literature. Fifth, the excess entropy scaling of the transport coefficients (self-diffusion, viscosity, and thermal conductivity) is reexamined using the contemporary datasets for the transport properties of Yukawa fluids. The results could be of particular interest in the context of complex (dusty) plasmas, colloidal suspensions, electrolytes, and other related systems with soft pairwise interactions.

Crossover from gas-like to liquid-like molecular diffusion in a simple supercritical fluid.

According to textbooks, no physical observable can be discerned allowing to distinguish a liquid from a gas beyond the critical point. Yet, several proposals have been put forward challenging this view and various transition boundaries between a gas-like and a liquid-like behaviour, including the so-called Widom and Frenkel lines, and percolation line, have been suggested to delineate the supercritical state space. Here we report observation of a crossover from gas-like (Gaussian) to liquid-like (Lorentzian) self-dynamic structure factor by incoherent quasi-elastic neutron scattering measurements on supercritical fluid methane as a function of pressure, along the 200 K isotherm. The molecular self-diffusion coefficient was derived from the best Gaussian (at low pressures) or Lorentzian (at high pressures) fits to the neutron spectra. The Gaussian-to-Lorentzian crossover is progressive and takes place at about the Widom line intercept (59 bar). At considerably higher pressures, a liquid-like jump diffusion mechanism properly describes the supercritical fluid on both sides of the Frenkel line. The present observation of a gas-like to liquid-like crossover in the self dynamics of a simple supercritical fluid confirms emerging views on the unexpectedly complex physics of the supercritical state, and could have planet-wide implications and possible industrial applications in green chemistry.

Thermal Density Fluctuations and Polymorphic Phase Transitions of Ethane (C2D6) in the Gas/Liquid and Supercritical States.

The phase behavior of the liquid C2D6 below and above the critical point was investigated using small-angle neutron scattering (SANS) in temperature and pressure ranges from 10 to 45 °C and 20 to 126 bar, respectively. The scattering of thermal fluctuations of the molecular density was determined and thus the gas-liquid and Widom lines. At the same time, we observed additional scattering of droplets of more densely packed C2D6 molecules above the gas-liquid line and in the supercritical fluid regime from just below the critical point for all temperatures at about ΔP = 10 bar above the Widom line. This line is interpreted as the Frenkel line. These results are consistent with our previous studies on CO2 and thus indicate a universal phase behavior for monomolecular liquids below and above the critical point. The interpretation of the Frenkel line as the lower limit of a polymorphic phase transition is in contrast to the usual interpretation as the limit of a dynamic process. The correlation lengths (ξ) of the thermal density fluctuations at the critical point and at the Widom line are determined between 20 and 35 Å and thus in the range of the droplet radius between 60 and 80 Å. These long-range fluctuations appear to suppress the formation of droplets, which can only form at about 10 bar above the critical point and the Widom line when ξ becomes smaller than 10 Å.

Mysteries of Water and Other Anomalous Liquids: “Slow” Sound and Relaxing Compressibility and Heat Capacity (Brief Review)

Reasons for the existence of “fast” sound at terahertz frequencies in various liquids have been analyzed. It has been shown that the fast sound speed is described well by the conventional formula from the theory of elasticity, where ρ is the density of a liquid andandare the bulk and shear moduli at the frequency ω, respectively. The excess of the speed of fast sound over the speed of normal sound in “normal” liquids is 10–20% and is almost completely determined by the contribution of the shear modulusat high frequencies, and vanishes on the Frenkel line. At the same time, the huge excess (50–120%) of the fast speed of sound over the speed of normal sound in some liquids (called “anomalous”), such as water and tellurium melt, is due mainly to the strong frequency dependence of the bulk modulus. Anomalously low relaxing bulk moduli were studied in our previous works for many oxide and chalcogenide glasses near smeared pressure-induced phase transitions. In anomalous liquids, smeared phase transitions also occur in a wide temperature and pressure region, which sharply reduces the bulk moduli and speeds of sound. Thus, the record large difference between speeds of fast and normal sound in anomalous liquids is due not to anomalously fast sound but to the fact that normal sound in such liquids is anomalously “slow” and bulk moduli are anomalously low. Ultrasonic studies of low- and high-density amorphous water ices show that their bulk moduli are indeed a factor of 4–5 higher than the bulk modulus of water. In addition, because of smeared phase transitions, the heat capacities of water and tellurium melt are a factor of 1.5–2 higher than those for normal liquids; i.e., anomalous liquids are characterized not only by an anomalous (nonmonotonic) behavior but also by anomalous magnitudes of physical quantities for most of the available measurement methods. A similar anomalous increase in the compressibility and heat capacity is observed for all fluids in the close vicinity of the liquid–gas critical point. In this case, anomalously fast sound is observed at terahertz frequencies, which is also due to a sharp increase in the bulk modulusat high frequencies. At the same time, high compressibility and heat capacity, as well as a large excess of the speed of fast sound over the speed of normal sound, for anomalous liquids and glasses near smeared phase transitions are not necessarily due to the proximity of critical points and occur in any scenario of the smeared phase transition.

From Atoms to Colloids: Does the Frenkel Line Exist in Discontinuous Potentials?

The Frenkel line has been proposed as a crossover in the fluid region of phase diagrams between a "nonrigid" and a "rigid" fluid. It is generally described as a crossover in the dynamical properties of a material and as such has been described theoretically using a very different set of markers from those with which is it investigated experimentally. In this study, we have performed extensive calculations using two simple yet fundamentally different model systems: hard spheres and square-well potentials. The former has only hardcore repulsion, while the latter also includes a simple model of attraction. We computed and analyzed a series of physical properties used previously in simulations and experimental measurements and discuss critically their correlations and validity as to being able to uniquely and coherently locate the Frenkel line in discontinuous potentials.

Revealing the supercritical dynamics of dusty plasmas and their liquidlike to gaslike dynamical crossover

Dusty plasmas represent a powerful playground to study the collective dynamics of strongly coupled systems with important interdisciplinary connections to condensed matter physics. Due to the pure Yukawa repulsive interaction between dust particles, dusty plasmas do not display a traditional liquid-vapor phase transition, perfectly matching the definition of a supercritical fluid. Using molecular dynamics simulations, we verify the supercritical nature of dusty plasmas and reveal the existence of a dynamical liquid-like to gas-like crossover which perfectly matches the salient features of the Frenkel line in classical supercritical fluids. We present several diagnostics to locate this dynamical crossover spanning from local atomic connectivity, shear relaxation dynamics, velocity autocorrelation function, heat capacity, and various transport properties. All these different criteria well agree with each other and are able to successfully locate the Frenkel line in both 2D and 3D dusty plasmas. In addition, we propose the unity ratio of the instantaneous transverse sound speed $C_T$ to the average particle speed $\bar{v}_{p}$, i.e., $C_T / \bar{v}_{p} = 1$, as a new diagnostic to identify this dynamical crossover. Finally, we observe an emergent degree of universality in the collective dynamics and transport properties of dusty plasmas as a function of the screening parameter and dimensionality of the system. Intriguingly, the temperature of the dynamical transition is independent of the dimensionality, and it is found to be always $20$ times of the corresponding melting point. Our results open a new path for the study of single particle and collective dynamics in plasmas and their interrelation with supercritical fluids in general.

Krypton and the Fundamental Flaw of the Lennard-Jones Potential.

We have performed a series of neutron scattering experiments on supercritical krypton. Our data and analysis allow us to characterize the Frenkel line crossover in this model monatomic fluid. The data from our measurements was analyzed using Empirical Potential Structure Refinement to determine the short- and medium-range structure of the fluids. We find evidence for several shells of neighbors which form approximately concentric rings of density about each atom. The ratio of second to first shell radius is significantly larger than in any crystal structure. Modeling krypton using a Lennard-Jones potential is shown to give significant errors, notably that the liquid is overstructured. The true potential appears to be longer ranged and with a softer core than the 6–12 powerlaws permit.

Fingerprints of the Crossing of the Frenkel and Melting Line on the Properties of High-Pressure Supercritical Water.

Using molecular dynamics simulations in combination with the two-phase thermodynamic model, we reveal novel characteristic fingerprints of the crossing of the Frenkel and melting line on the properties of high-pressure water at a near-critical temperature (1.03Tc). The crossing of the Frenkel line at about 1.17 GPa is characterized by a crossover in the rotational and translational entropy ratio Srot/Strans, indicating a change in the coupling between translational and rotational motions which is also reflected in the shape of the rotational density of states. The observed isosbestic points in the translational and rotational density of states are also blue-shifted at density and pressure conditions higher than the ones corresponding to the Frenkel line. The first-order phase transition from a rigid liquid to a face-centered cubic plastic crystal phase at about 8.5 GPa is reflected in the discontinuous changes in the translational and rotational entropy, particularly in the significant increase of the ratio Srot/Strans. A noticeable discontinuous increase of the dielectric constant has also been revealed when crossing this melting line, which is attributed to the different arrangement of the water molecules in the plastic crystal phase. The reorientational dynamics in the plastic crystal phase is faster in comparison with the "rigid" liquid-like phase, but it remains unchanged upon a further pressure increase in the range of 8.5-11 GPa.

A general model for isochoric heat capacity of matter in different states by introducing thermodynamic dimension concept

Using the Maxwell-Boltzmann distribution function and considering Frenkel's theory of liquids; a substance is approached as a fractal lattice. We introduce a new concept that we call it thermodynamic dimension DT to generalize both Einstein and Debye models, so that both models are a special case of the general model (DT = 3). The thermodynamic dimension DT of a fluid is a dimensionless quantity whose value can be a number between zero and three (0 ≤ DT ≤ 3). In a wide range of temperature and pressure comparison of calculated results with experimental data for isochoric heat capacities in dense region show good agreement in the studied fluids. Based on the obtained results, we illustrate existence of the principle of the corresponding states for simple fluids. Finally, in addition to introducing a new condition (DT = 1/2) to plotting the Frenkel line, we predict solid-like features for around of the critical point.

Frenkel Line in Nitrogen Terminates at the Triple Point.

Recent studies on supercritical nitrogen revealed clear changes in structural markers and dynamical properties when the coordination number approaches its maximum value. The line in P and T space where these changes occur is referred to as the Frenkel line. Here, we qualitatively reproduce such changes in the supercritical regime using the popular "optimized potential for liquid simulation" (OPLS) classical force field for molecular dynamics. Unfortunately, at 160 K, OPLS nitrogen predicts sublimation rather than producing a liquid phase; therefore, we developed our own force field to achieve quantitative agreement with experimental data. We confirm the asymptotic behavior of the coordination number on crossing the Frenkel line and note an associated change in the diffusion constant, consistent with the non-rigid to rigid liquid-like character of the "transition". The simulations allow us to track the Frenkel line to subcritical temperatures and demonstrate that it terminates at the triple point. This establishes the experimentally measurable changes, which could unequivocally determine the Frenkel line in other systems.

On the Different Faces of the Supercritical Phase of Water at a Near-Critical Temperature: Pressure-Induced Structural Transitions Ranging from a Gaslike Fluid to a Plastic Crystal Polymorph.

The present study reports a systematic analysis of a wide variety of structural, thermodynamic, and dynamic properties of supercritical water along the near-critical isotherm of T = 1.03Tc and up to extreme pressures, using molecular dynamics and Monte Carlo simulations. The methodology employed provides solid evidence about the existence of a structural transition from a liquidlike fluid to a compressed, tightly packed liquid, in the density and pressure region around 3.4ρc and 1.17 GPa, introducing an alternative approach to locate the crossing of the Frenkel line. Around 8.5 GPa another transition to a face-centered-cubic plastic crystal polymorph with density 5.178ρc is also observed, further confirmed by Gibbs free energy calculations using the two-phase thermodynamic model. The isobaric heat capacity maximum, closely related to the crossing of the Widom line, has also been observed around 0.8ρc, where the local density augmentation is also maximized. Another structural transition has been observed at 0.2ρc, related to the transformation of the fluid to a dilute gas at lower densities. These findings indicate that a near-critical isotherm can be divided into different domains where supercritical water exhibits distinct behavior, ranging from a gaslike one to a plastic crystal one.

Structural Markers of the Frenkel Line in the Proximity of Widom Lines.

We have performed a neutron scattering experiment on supercritical fluid nitrogen at 160 K (1.27 TC) over a wide pressure range (7.8 MPa/0.260 g/mL-125 MPa/0.805 g/mL). This has enabled us to study the process by which nitrogen changes from a fluid that exhibits gaslike behavior to one that exhibits rigid liquidlike behavior at a temperature close to, but above, the critical temperature by crossing the Widom lines followed by the Frenkel line on pressure (density) increase. We find that the Frenkel line transition is indicated by a transition to a regime of rigid liquidlike behavior in which the coordination number remains constant within error, in agreement with our previous work at 300 K. The Frenkel line transition takes place at approximately the same density at 160 and 300 K. The data do not conclusively show an additional transition at the location of the known Widom lines. We find that behavior remains gaslike until the Frenkel line is crossed and our data support the hypothesis that Widom line transitions are density increase-driven.

Calculation of self-diffusion coefficients in supercritical carbon dioxide using mean force kinetic theory.

This paper presents an application of mean force kinetic theory (MFT) to the calculation of the self-diffusivity of CO2 in the supercritical fluid regime. Two modifications to the typical application of MFT are employed to allow its application to a system of molecular species. The first is the assumption that the inter-particle potential of mean force can be obtained from the molecule center-of-mass pair correlation function, which in the case of CO2 is the C-C pair correlation function. The second is a new definition of the Enskog factor that describes the effect of correlations at the surface of the collision volume. The new definition retains the physical picture that this quantity represents a local density increase, resulting from particle correlations, relative to that in the zero density homogeneous fluid limit. These calculations are facilitated by the calculation of pair correlation functions from molecular dynamics (MD) simulations using the FEPM2 molecular CO2 model. The self-diffusivity calculated from theory is in good agreement with that from MD simulations up to and slightly beyond the density at the location of the Frenkel line. The calculation is compared with and is found to perform similarly well to other commonly used models but has a greater potential for application to systems of mixed species and to systems of particles with long range interatomic potentials due to electrostatic interactions.

Crossover of dynamical instability and chaos in the supercritical state.

We calculate the maximal Lyapunov exponent for a bulk system of 256 Lennard-Jones particles in constant energy molecular dynamics simulations deep into the supercritical state. We find that the maximal Lyapunov exponent undergoes a crossover and that this crossover coincides with the dynamical crossover at the Frenkel line from liquid physics. We explain this crossover in terms of two different contributions to dynamical instability: diffusion in the liquidlike state below the Frenkel line and collisions in the gaslike state above. These results provide insight into the phase-space dynamics far from the melting line and densities where rare-gas approximation are inapplicable.

Modeling of liquid internal energy and heat capacity over a wide pressure–temperature range from first principles

Recently, there have been significant theoretical advances in our understanding of liquids and dense supercritical fluids based on their ability to support high frequency transverse (shear) waves. Here, we have constructed a new computer model using these recent theoretical findings (the phonon theory of liquid thermodynamics) to model liquid internal energy across a wide pressure–temperature range. We have applied it to a number of real liquids in both the subcritical regime and the supercritical regime, in which the liquid state is demarcated by the Frenkel line. Our fitting to experimental data in a wide pressure–temperature range has allowed us to test the new theoretical model with hitherto unprecedented rigor. We have quantified the degree to which the prediction of internal energy and heat capacity is constrained by the different input parameters: the liquid relaxation time (initially obtained from the viscosity), the Debye wavenumber, and the infinite-frequency shear modulus. The model is successfully applied to output the internal energy and heat capacity data for several different fluids (Ar, Ne, N2, and Kr) over a range of densities and temperatures. We find that the predicted heat capacities are extremely sensitive to the values used for the liquid relaxation time. If these are calculated directly from the viscosity data, then, in some cases, changes within the margins of the experimental error in the viscosity data can cause the heat capacity to exhibit a completely different trend as a function of temperature. Our code is computationally inexpensive, and it is available for other researchers to use.

Polymorphic phase transition in liquid and supercritical carbon dioxide

We present experiments on molecular density fluctuations in liquid and supercritical (SC) CO2 using small-angle neutron scattering. Thermal density fluctuations in SC-CO2 determine susceptibility and correlation length identifying the Widom line at their maxima. Droplet formation occurs at the gas–liquid line and between 20 and 60 bar above the Widom line, the corresponding borderline identified as the Frenkel line. The droplets start to form spheres of constant radius of ≈ 45 Å and transform into rods and globules at higher pressure. Droplet formation represents a liquid–liquid (polymorphic) phase transition of the same composition but different density, whose difference defines its order parameter. Polymorphism in CO2 is a new observation stimulating interesting discussions on the topics of gas-like to liquid-like transition in SC fluids and polymorphism since CO2 represents a “simple” van der Waals liquid in contrast to water, which is the most widely studied liquid showing polymorphism in its supercooled state.

Pronounced structural crossover in water at supercritical pressures

There have been ample studies of the many phases of H2O in both its solid and low pressure liquid states, and the transitions between them. Using molecular dynamics simulations we address the hitherto unexplored deeply supercritical pressures, where no qualitative transitions are thought to take place and where all properties are expected to vary smoothly. On the basis of these simulations we predict that water at supercritical pressures undergoes a structural crossover across the Frenkel line at pressures as high as 45 times the critical pressure. This provides a new insight into the water phase diagram and establishes a link between the structural and dynamical properties of supercritical water. Specifically, the crossover is demonstrated by a sharp and pronounced at low pressures, and smooth at high pressures, signified by changes in the pair distribution functions and local coordination which coincide with the dynamical transition (the loss of all oscillatory molecular motion) at the Frenkel line on the phase diagram.

Between supercritical liquids and gases – Reconciling dynamic and thermodynamic state transitions

Experimental, computational, and theoretical results have shown that the notion of a homogeneous supercritical state space has to be replaced with distinct liquid-like and gas-like regions, divided by a cross-over line. Several such cross-over lines have been proposed, such as the Frenkel line, the Fisher-Widom line, and the Widom line. We use thermodynamics arguments, molecular dynamics (MD) simulations, and experimental data to investigate the relation between these lines. This work proposes a new interpretation of the Widom line based on the curvature of the Gibbs free energy, showing that the supercritical cross-over can be evaluated as a projection of the subcritical phase transition from a liquid to an ideal gas state to supercritical conditions. We show that the cross-over across the Widom line should not be regarded as instantaneous, but instead as spreading over a finite temperature interval. The thermodynamic character of the Widom line becomes negligible at reduced pressures p/pcr > 3 and disappears completely at higher pressures p/pcr > 10. We find evidence that measured transitions attributed to the Widom line do in fact match the Frenkel line better. In this way, we suggest a consistent view of the supercritical state space and resolve apparent contradictions.

Experimental and modeling evidence for structural crossover in supercritical CO_{2}.

The physics of supercritical states is understood to a much lesser degree compared to subcritical liquids. Carbon dioxide, in particular, has been intensely studied, yet little is known about the supercritical part of its phase diagram. Here, we combine neutron scattering experiments and molecular dynamics simulations and demonstrate the structural crossover at the Frenkel line. The crossover is seen at pressures as high as 14 times the critical pressure and is evidenced by changes of the main features of the structure factor and pair distribution functions.