arXiv subjects

V. V. Brazhkin

Publications and source records attributed to V. V. Brazhkin.

At least 37 records · Page 2Linked to original sources

arXiv2019

Thermodynamic heterogeneity and crossover in the supercritical state of matter

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.

cond-mat.stat-mech↗

arXiv2019

The nature of collective excitations and their crossover at extreme supercritical conditions

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.

cond-mat.stat-mech↗

arXiv2018

Anomalous behavior of dispersion curves in water-like systems and water

In the present paper we consider dispersion curves of longitudinal excitations of a model core-softened liquid and SPC/E model of water. We show that both systems demonstrate anomalous behavior of the excitation frequencies: the frequencies of the excitations can decrease with temperature along isochors, while in normal liquids they should increase. This observation allows to introduce one more water anomaly - anomalous dependence of excitation frequencies on temperature.

cond-mat.soft↗

arXiv2018

Organic crystalline polymers: structural properties and way to synthesis under high pressure

We consider different structures, which can be obtained by polymerization of aromatic organic molecules under high pressures. These 2D and 3D covalently bonded organic polymers and their functionalization can pave the way to production of energy storage and conversion devices. High-pressure synthesis might serve as a useful hint for production of these structures and their functionalized analogs by means of wet chemical synthesis.

cond-mat.mtrl-sci↗

arXiv2017

Crossover between liquid-like and gas-like behaviour in CH4 at 400 K

We report experimental evidence for a crossover between a liquid-like state and a gas-like state in fluid methane (CH4). This crossover is observed in all of our experiments, up to 397 K temperature; 2.1 times the critical temperature of methane. The crossover has been characterized with both Raman spectroscopy and X-ray diffraction in a number of separate experiments, and confirmed to be reversible. We associate this crossover with the Frenkel line - a recently hypothesized crossover in dynamic properties of fluids extending to arbitrarily high pressure and temperature, dividing the phase diagram into separate regions where the fluid possesses liquid-like and gas-like properties. On the liquid-like side the Raman-active vibration increases in frequency linearly as pressure is increased, as expected due to the repulsive interaction between adjacent molecules. On the gas-like side this competes with the attractive Van der Waals potential leading the vibration frequency to decrease as pressure is increased.

cond-mat.stat-mech↗

arXiv2017

Supercritical Grüneisen parameter and its universality at the Frenkel line

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 Grüneisen parameter γ 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 γ 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 γ 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.

cond-mat.soft↗

arXiv2017

A novel anomalous region of water

Water is the most important liquid in the Universe. At the same time it is the most anomalous liquid. It demonstrates several dozens of anomalies, among which are density anomaly, diffusion anomaly etc. Anomalous behavior of water is a topic numerous publications. However, most of the publications investigate the anomalous behavior of water in the vicinity of critical points: the liquid-gas critical point and the second hypothetical critical point in supercooled region. Here we analyze experimental data on such properties of water as heat capacity, speed of sound, dynamic viscosity and thermal conductivity. We show that these properties demonstrate anomalous maxima and minima in a region which is far from both critical points. Therefore, we find a novel region of anomalous properties of water (anomalous triangle) which cannot be related to critical fluctuations. We also perform a molecular dynamics simulations of this region with two common water models - SPC/E and TIP4P - and show that these models fail to describe the novel anomalous region.

cond-mat.soft↗

arXiv2017

Emergence and evolution of $k$-gap in spectra of liquid and supercritical states

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.

cond-mat.soft↗

arXiv2017

Experimental evidence of the Frenkel line in supercritical neon

Recent research suggests that the supercritical state consists of liquidlike and gaslike states where particle dynamics and key system properties are qualitatively different. We report experimental evidence of the structural crossover in supercritical neon at pressure and temperature conditions significantly exceeding the critical point values: 250$\,P_c$ and 6.6$\,T_c$. The experimental results show a crossover of the medium-range order structure evidenced by the change of the structure factor with pressure. We also observe the crossover of the short-range order structure indicated by changes in the coordination number. The relative width of the crossover is fairly narrow and is smaller than 10-12 \% in pressure and temperature. By comparing our experimental results with molecular dynamics simulations, we suggest that the observed crossover can be attributed to the Frenkel line and discuss the relationship between the structural crossover and qualitative changes of dynamical and thermodynamic properties of supercritical matter.

cond-mat.mtrl-sci↗

arXiv2017

Direct links between dynamical, thermodynamic and structural properties of liquids: modelling results

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.

cond-mat.soft↗

arXiv2016

Bulk graphanes synthesized from benzene and pyridine

We report a high-pressure high-temperature synthesis of several millimeter-sized samples of bulk graphanes with the composition C-H(D) from benzene and graphene-derivative C-H-N$_{0.2}$ from pyridine. X-ray diffraction, transmission electron microscopy, and infrared spectroscopy of new materials reveal relatively large (several nanometers in size) crystalline grains of an sp3-bonded graphane lattice (3-cycle-4-step, the orthorhombic structure with Pbca space group and parameters a = 9.5-9.8, b = 8.9-9.1, c = 17.1-17.3 $Å$). The main hydrogen groups in samples are C-H groups connected by aliphatic bonds. The synthesized graphanes at atmospheric pressure are stable up to 500 C. The macroscopic density of CH samples is 1.5-1.57 g cm$^{-3} $ and the refractive index is 1.78-1.80. The absorption spectra of samples with a high degree of crystallization exhibits a weak absorption maximum at 2.8 eV, which is responsible for the yellow-orange color, large absorption maximum at 4 eV and an absorption edge associated with the width of the optical gap at 5.2 eV. The bulk modulus (30-37 GPa) and shear modulus (15-18 GPa) of the fabricated samples, as well as their hardness (1-1.5 GPa), are about twice as high as the respective values for polycrystalline graphite. The solution of metalorganic complexes in benzene and pyridine makes it possible to obtain doped graphanes, which can have extraordinary electron transport and magnetic properties.

cond-mat.mtrl-sci↗

arXiv2016

Comment on: "The Frenkel Line: a direct experimental evidence for the new thermodynamic boundary"

In a recent publication (D. Bolmatov et al. Sci.Rep. 5, 15850 (2015)) the experimental observation of structural transformations on crossing the Frenkel line in supercritical argon is claimed. Here we show that no experimental evidence of the structural transformation was presented. The reported experimental observations which Bolmatov et al. claim as evidence of a transition across the Frenkel line are instead due to the irregularity of the experimental (P,T) path in their work.

cond-mat.soft↗

arXiv2016

Anomalous vacuum energy and stability of a quantum liquid

We show that the vacuum (zero-point) energy of a low-temperature quantum liquid is a variable property which changes with the state of the system, in notable contrast to the static vacuum energy in solids commonly considered. We further show that this energy is inherently anomalous: it decreases with temperature and gives negative contribution to system's heat capacity. This effect operates in an equilibrium and macroscopic system, in marked contrast to small or out-of-equilibrium configurations discussed previously. We find that the negative contribution is over-compensated by the positive term from the excitation of longitudinal fluctuations and demonstrate how the overall positive heat capacity is related to the stability of a condensed phase at the microscopic level.

cond-mat.stat-mech↗

arXiv2015

Collective modes and thermodynamics of the liquid state

Strongly interacting, dynamically disordered and with no small parameter, liquids took a theoretical status between gases and solids. We review different approaches to liquids and propose that liquids do not need classifying in terms of their proximity to gases and solids. Instead, they are a unique system in their own class with a notably mixed dynamical state in contrast to pure dynamical states of solids and gases. We start with explaining how the first-principles approach to liquids is an intractable, exponentially complex problem of coupled non-linear oscillators with bifurcations. This is followed by a reduction of the problem based on liquid relaxation time $τ$ representing non-perturbative treatment of strong interactions. On the basis of $τ$, solid-like high-frequency modes are predicted and we review related recent experiments. We demonstrate how these modes can be derived by generalizing either hydrodynamic or elasticity equations. We comment on the historical trend to approach liquids using hydrodynamics and compare it to an alternative solid-like approach. We subsequently discuss how collective modes evolve with temperature and how this affects liquid energy and other properties such as fast sound. Here, our emphasis is on real, rather than model, liquids. Highlighting the dominant role of high-frequency modes for liquid energy, we review a wide range of liquids: subcritical low-viscous liquids, supercritical state with two different dynamical and thermodynamic regimes separated by the Frenkel line, highly-viscous liquids and liquid-glass transition. We also discuss liquid-liquid phase transitions where the solid-like properties of liquids have become further apparent. We then discuss gas-like and solid-like approaches to quantum liquids and persisting theoretical problems. We list areas where interesting insights may appear and continue the extraordinary liquid story.

cond-mat.soft↗

arXiv2015

Direct evidence for strong crossover of collective excitations and positive sound dispersion in the supercritical state

Supercritical state has been viewed as an intermediate state between gases and liquids with largely unknown physical properties. Here, we address the important ability of supercritical fluids to sustain collective excitations. We directly study propagating modes on the basis of correlation functions calculated from extensive molecular dynamics simulations, and find that the supercritical system sustains propagating solid-like transverse modes below the Frenkel line but becomes devoid of transverse modes above the line where it supports longitudinal modes only. Important thermodynamic implications of this finding are discussed. We directly detect positive sound dispersion (PSD) below the Frenkel line where transverse modes are operative, quantitatively explain its magnitude on the basis of transverse and longitudinal velocities. PSD disappears above the Frenkel line which therefore demarcates the supercritical phase diagram into two areas where PSD does and does not operate.

cond-mat.stat-mech↗

arXiv2015

Dynamical Crossover in Supercritical Core-Softened Fluids

It is well known that some liquids can demonstrate anomalous behavior. Interestingly, this be- havior can be qualitatively reproduced with simple core-softened isotropic pair-potential systems. Although anomalous properties of liquids usually take place at low and moderate temperatures it was recently recognized that many important phenomena can appear in supercritical fuids. However, no studies of supercritical behavior of core-softened fuids is reported. This paper reports a study of dynamical crossover in supercritical core-softened systems. The crossover line is calculated from three different criteria and good agreement between them is observed. It is found that the behavior of the dynamical crossover line of core-softened systems is quite complex due to its quasi-binary nature.

cond-mat.stat-mech↗

arXiv2015

Diamond monohydride: The most stable three-dimensional hydrocarbon

Most of hydrocarbons are either molecular structures or linear polymeric chains. Discovery of graphene and manufacturing of its monohydride -- graphane incite interest in search for three-dimensional hydrocarbon polymers. However up to now all hypothetical hydrocarbon lattices significantly lose in energy to stacked graphane sheets and solid benzene. We propose completely covalently bonded solid carbon monohydride whose density significantly exceeds one of its isomers (graphane, cubane, solid benzene). Ab-initio calculation demonstrates that the cohesion energy of this structure at least is not worse than the energy of graphane and benzene. In some aspect the crystal structure of hydrocarbon presented can be regarded as a sublattice of diamond, but with the symmetry of P-3 space group (lattice parameters a ~ 6.925 A, c ~ 12.830 A) and Z=42 formula units per unit cell. This structure (if synthesized) may turn out to be interesting to applications.

cond-mat.mtrl-sci↗

arXiv2015

Solid-state diffusion in amorphous zirconolite

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.

cond-mat.mtrl-sci↗