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A hallmark of a thermodynamic phase transition is the qualitative change of system thermodynamic properties such as energy and heat capacity. On the other hand, no phase transition is thought to operate in the supercritical state of matter and, for this reason, it was believed that supercritical thermodynamic properties vary smoothly and without any qualitative changes. Here, we perform extensive molecular dynamics simulations in a wide temperature range and find that a deeply supercritical state is thermodynamically heterogeneous, as witnessed by different temperature dependence of energy, heat capacity and its derivatives at low and high temperature. The evidence comes from three different methods of analysis, two of which are model-independent. We propose a new definition of the relative width of the thermodynamic crossover and calculate it to be in the fairly narrow relative range of 13-20\%. On the basis of our results, we relate the crossover to the supercritical Frenkel line.

Physical properties of an interacting system are governed by collective excitations, but their nature at extreme supercritical conditions is unknown. Here, we present direct evidence for propagating solid-like longitudinal phonon-like excitations with wavelengths extending to interatomic separations deep in the supercritical state at temperatures up to 3,300 times the critical temperature. We observe that the crossover of dispersion curves develops at $k$ points reducing with temperature. We interpret this effect as the crossover from the collective phonon to the collisional mean-free path regime of particle dynamics and find that the crossover points are close to both the inverse of the shortest available wavelength in the system and to the particle mean free path inferred from experiments and theory. Notably, both the shortest wavelength and mean free path scale with temperature with the same power law, lending further support to our findings.

We study thermo-mechanical properties of matter at extreme conditions deep in the supercritical state, at temperatures exceeding the critical one up to four orders of magnitude. We calculate the Gr\"{u}neisen parameter {\gamma} and find that it decreases with temperature from 3 to 1 on isochores depending on the density. Our results indicate that from the perspective of thermo-mechanical properties, the supercritical state is characterized by the wide range of {\gamma} which includes the solid-like values - an interesting finding in view of the common perception of the supercritical state as being an intermediate state between gases and liquids. We rationalize this result by considering the relative weights of oscillatory and diffusive components of the supercritical system below the Frenkel line. We also find that {\gamma} is nearly constant at the Frenkel line above the critical point and explain this universality in terms of pressure and temperature scaling of system properties along the lines where particle dynamics changes qualitatively.

The existence of the phonon-roton minimum has been widely observed for both the solid and liquid phases but so far there is no sufficient theoretical explanation of its origin. In this paper we use a range of techniques to study the dynamics and short-range order for a range of simple materials in their crystalline, amorphous and liquid phases. We perform inelastic neutron scattering (INS) experiments of polycrystalline and liquid barium to study the high-frequency dynamics and understand the mechanisms underlying the atomic motion. Moreover we perform INS simulations for crystals and supercooled liquids, compare the collective excitation spectra and identify similarities. We perform molecular dynamics (MD) simulations for the same materials and present results of population and bond angle distribution showing a short-range order dependence of the different phases, expanding the current knowledge in literature. Finally, we support our findings with a theoretical explanation of the origin of the phonon-roton minima which is observed in both solids and liquids. We study this as a classical phenomenon and we base our explanation on short range interatomic interactions.

Fundamental understanding of strongly-interacting systems necessarily involves collective modes, but their nature and evolution is not generally understood in dynamically disordered and strongly-interacting systems such as liquids and supercritical fluids. We report the results of extensive molecular dynamics simulations and provide direct evidence that liquids develop a gap in solid-like transverse spectrum in the reciprocal space, with no propagating modes between zero and a threshold value. In addition to the liquid state, this result importantly applies to the supercritical state of matter. We show that the emerging gap increases with the inverse of liquid relaxation time and discuss how the gap affects properties of liquid and supercritical states.

We develop an approach to liquid thermodynamics based on collective modes. We perform extensive molecular dynamics simulations of noble, molecular and metallic liquids and provide the direct evidence that liquid energy and specific heat are well-described by the temperature dependence of the Frenkel (hopping) frequency. The agreement between predicted and calculated thermodynamic properties is seen in the notably wide range of temperature spanning tens of thousands of Kelvin. The range includes both subcritical liquids and supercritical fluids. We discuss the structural crossover and inter-relationships between structure, dynamics and thermodynamics of liquids and supercritical fluids., Comment: 10 pages, 6 figures

We discuss how structural disorder and amorphization affects solid-state diffusion, and consider zirconolite as a currently important case study. By performing extensive molecular dynamics simulations, we disentangle the effects of amorphization and density, and show that a profound increase of solid-state diffusion takes place as a result of amorphization. Importantly, this can take place at the same density as in the crystal, representing an interesting general insight regarding solid-state diffusion. We find that decreasing the density in the amorphous system increases pre-factors of diffusion constants, but not decreasing the activation energy. We also find that atomic species in zirconolite are affected differently by amorphization and density change. Our microscopic insights are relevant for understanding how solid-state diffusion changes due to disorder and for building predictive models of operation of materials to be used to encapsulate nuclear waste.

A new dynamic line, the Frenkel line, has recently been proposed to separate the supercritical state into rigid-liquid and non-rigid gas-like uid. The location of Frenkel line on the phase diagram is unknown for real uids. Here, we map the Frenkel line for three important systems: CO2, H2O and CH4. This provides an important demarcation on the phase diagram of these systems, the demarcation that separates two distinct physical states with liquid-like and gas-like properties. We find that the Frenkel line can have similar trend as the melting line above the critical pressure. Moreover, we discuss the relationship between unexplained solubility maxima and Frenkel line, and propose that the Frenkel line corresponds to the optimal conditions for solubility.

Slow flow of the viscous liquid is a thought-provoking experiment that challenges students, academics and public to think about some fundamental questions in modern science. In the Queensland demonstration, the world-longest running experiment earning the Ig Nobel prize, one drop of pitch takes about 10 years to fall, leading to problems of actually observing the drops. Here, we describe our recent demonstration of slowly-flowing bitumen where appreciable flow is observed on the time scale of months. The experiment is free from dissipative heating effects and has the potential to improve the accuracy of measurement. Bitumen viscosity was calculated by undergraduate students during the summer project. The worldwide access to the running experiment is provided by webcams uploading the images to a dedicated website, enhancing student education experience and promotion of science. This demonstration serves as an attractive student education exercise and stimulates the discussion of fundamental concepts and hotly debated ideas in modern physics research: difference between solids and liquids, the nature of liquid-glass transition, emergence of long time scales in a physical process, and the conflict between human intuition and physical reality.

We propose a new simple way to evaluate the effect of anharmonicity on a system's thermodynamic functions such as heat capacity. In this approach, the contribution of all potentially complicated anharmonic effects to constant-volume heat capacity is evaluated by one parameter only, the coefficient of thermal expansion. Importantly, this approach is applicable not only to crystals but also to glasses and viscous liquids. To support this proposal, we perform molecular dynamics simulations of several crystalline and amorphous solids as well as liquids, and find a good agreement between results from theory and simulations. We observe an interesting non-monotonic behavior of liquid heat capacity with a maximum, and explain this effect as a result of competition between anharmonicity at low temperature and decreasing number of transverse modes at high temperature.

We report the results of the X-ray diffraction study of B2O3 glass in the pressure interval up to 10 GPa in the 300-700 K temperature range, the results of in-situ volumetric measurements of the glass at pressures up to 9 GPa at room temperature, and first-principles simulations data at pressures up to 250GPa. The behavior of B2O3 glass under pressure can be described as two broad pressure-overlapping transitions. The first transition starts at P > 1 GPa and proceeds without any changes in thecoordination number of the boron atoms; the other one starts at P > 5 GPa and is accompanied by a gradual increase of coordination number. The second transition is completely reversible; the residual densification of the B2O3 glass after decompression is associated with the incomplete reversibility of the first transformation. The fraction of boron atoms transferred to the 4-coordination state in the glass at P < 10 GPa is much smaller than was assumed from indirect experimental data [4], but is considerably larger (by tens of times) than was previously suggested by the classical molecular dynamics simulations [5,6]. The observed transformations under both compression and decompression are quite broad, contrary to the assumption in Ref. [7]. On the basis of ab-initio results, we also predict the one more transformation under higher pressures to a super-dense phase, in which B atoms become 5- and 6-fold coordinated.