arXiv subjects

Maxim Bykov

Publications and source records attributed to Maxim Bykov.

At least 19 recordsLinked to original sources

arXiv2026

Two New Molecular Nitrogen Phases near Megabar Pressures

Molecular nitrogen exhibits remarkable structural diversity near the polymeric transition, where multiple phases are metastable. Here, we report two new molecular phases. The first, $t\zeta$-N$_2$, is a polytype of monoclinic $C2/c$ $\zeta$-N$_2$, characterized by a tripled $c$ axis and 96 atoms per unit cell. The second, $\xi$-N$_2$, is a previously unreported hexagonal phase ($P6cc$) containing 112 atoms per unit cell. Both phases were synthesized in a diamond anvil cell by laser heating $\zeta$-N$_2$ to 1800--2500~K at pressures of 78--98~GPa. Their crystal structures were determined using single-crystal X-ray diffraction, corroborated by Raman spectroscopy, and supported by first-principles calculations. The $t\zeta$-N$_2$ phase likely corresponds to the previously reported $\kappa$-N$_2$ phase.

cond-mat.mtrl-sci↗

arXiv2026

Hydrogen uptake and hydride formation in Al$_x$CoCrFeNi high-entropy alloys: First-principles, universal-potential, and experimental study

Hydrogen uptake in complex multicomponent alloys, including high-entropy alloys (HEAs), governs both hydrogen storage capacity and resistance to hydrogen-induced degradation. We combine high-pressure experiments, density-functional theory (DFT), and a GRACE universal interatomic potential to investigate hydrogen absorption in Al$_{0.3}$CoCrFeNi and Al$_3$CoCrFeNi HEAs. In H$_2$ as a pressure-transmitting medium, the FCC Al$_{0.3}$CoCrFeNi alloy forms hydrides at ambient temperature above 3 GPa, whereas the Al-rich B2 Al$_3$CoCrFeNi alloy shows no evidence of hydride formation even upon heating at pressures up to 50 GPa. Experiments and calculations show that aluminum suppresses hydrogen uptake by increasing solution energies and destabilizing interstitial sites. The universal potential, employed in the calculations and pretrained on large DFT databases, closely reproduces DFT energetics and demonstrates transferability from the dilute limit to the hydride-forming regime. Simulations further disentangle the roles of local ordering, volume changes, composition, and crystal structure. Overall, our results indicate that hydrogen solubility in Al-containing HEAs is governed primarily by composition, with Al-driven B2 ordering as a strong secondary effect.

cond-mat.mtrl-sci↗

arXiv2025

Hydrogen-rich hydrate at high pressures up to 104 GPa

Gas hydrates are considered fundamental building blocks of giant icy planets like Neptune and similar exoplanets. The existence of these materials in the interiors of giant icy planets, which are subject to high pressures and temperatures, depends on their stability relative to their constituent components. In this study, we reexamine the structural stability and hydrogen content of hydrogen hydrates, (H2O)(H2)n, up to 104 GPa, focusing on hydrogen-rich materials. Using synchrotron single-crystal X-ray diffraction, Raman spectroscopy, and first-principles theoretical calculations, we find that the C2-filled ice phase undergoes a transformation to C3-filled ice phase over a broad pressure range of 47 - 104 GPa at room temperature. The C3 phase contains twice as much molecular H2 as the C2 phase. Heating the C2-filled ice above approximately 1500 K induces the transition to the C3 phase at pressures as low as 47 GPa. Upon decompression, this phase remains metastable down to 40 GPa. These findings establish new stability limits for hydrates, with implications for hydrogen storage and the interiors of planetary bodies.

cond-mat.mtrl-sci↗

arXiv2024

Polymorphism of monatomic iodine

We applied synchrotron single-crystal X-ray diffraction in a diamond anvil cell at 48-51 GPa and first-principles theoretical calculations to study the crystal structure of solid atomic iodine at high pressure. We report the synthesis of two phases of atomic iodine at 48-51 GPa via laser heating of I-N2 mixtures. Unlike the familiar monatomic I4/mmm structure, which consists of crystallographically equivalent atoms, a new Pm-3n structure is of inclusion type, featuring two distinct kinds of atoms: a central detached one and peripheral ones forming the linear chains. Moreover, we observe crystallization of the familiar high-pressure face centered cubic (fcc) structure, albeit at much lower pressures compared to cold compressed iodine. The discovery of Pm-3n structure in iodine marks an important step in understanding of the pressure induced phase transition sequence in halogens.

cond-mat.mtrl-sci↗

arXiv2024

High entropy alloys and their affinity to hydrogen: from Cantor to platinum group elements alloys

Properties of high entropy alloys are currently in the spotlight due to their promising applications. One of the least investigated aspects is the affinity of these alloys to hydrogen, its diffusion and reactions. In this study we apply high-pressure at ambient temperature and investigate stress-induced diffusion of hydrogen into the tructure of high entropy alloys HEA including the famous Cantor alloy as well as less known, but nevertheless important platinum group PGM alloys. By applying X-ray diffraction to samples loaded into diamond anvil cells we perform a comparative investigation of these HEA alloys in Ne and H2 pressure-transmitting media. Surprisingly, even under stresses far exceeding conventional industrial processes both Cantor and PGM alloys show exceptional resistance to hydride formation, on par with widely used industrial grade CuBe alloys. Our observations inspire optimism for practical HEA applications in hydrogen-relevant industry and technology e.g. coatings, etc, particularly those related to transport and storage.

cond-mat.mtrl-sci↗

arXiv2023

Polytypism of Incommensurately Modulated Structures of Crystalline Bromine upon Molecular Dissociation under High Pressure

Polytypism of incommensurately modulated structures was hitherto unobserved. Here, we found the phenomenon in simple halogen systems of bromine and iodine upon molecular dissociation in the solids under pressure. Single-crystal synchrotron X-ray diffraction in laser heated diamond anvil cells pressurised up to 112 GPa revealed a number of allotropes of bromine and iodine including polytypes of Br-III{\gamma} (Fmmm(00{\gamma})s00) with {\gamma} varying within 0.18 to 0.3.

cond-mat.mtrl-sci↗

arXiv2023

Structural diversity of molecular nitrogen on approach to polymeric states

Nitrogen represents an archetypal example of material exhibiting a pressure driven transformation from molecular to polymeric state. Detailed investigations of such transformations are challenging because of a large kinetic barrier between molecular and polymeric structures, making the transformation largely dependent on kinetic stimuli. In the case of nitrogen, additional complications occur due to the rich polymorphism in the vicinity of the transition. Here, we report the observation of both molecular (\theta) and polymeric (BP) phases, crystallized upon temperature quenching of fluid nitrogen to room temperature at 97-114 GPa. Synchrotron single-crystal X-ray diffraction, Raman spectroscopy, and first-principles theoretical calculations have been used for diagnostics of the phases and determination of their structure and stability. Molecular \theta-nitrogen is the most stable among molecular phases bordering the stability field of polymeric phases, partially settling a previously noted discrepancy between theory and experiment concerning the thermodynamic stability limit of molecular phases.

cond-mat.mtrl-sci↗

arXiv2023

Assessing the stability fields of molecular and polymeric CO2

We investigated the stability of polymeric CO2 over a wide range of pressures, temperatures, and chemical environments. We find that the I-42d polymeric structure, consisting of a three-dimensional network of corner sharing CO4 tetrahedra, forms at 40-140 GPa and from a CO-N2 mixture at 39 GPa. An exceptional stability field of 0 to 286 GPa and 100 to 2500 K is documented for this structure, making it a viable candidate for planetary interiors. The stability of the tetrahedral polymeric motif of CO2-V is a consequence of the rigidity of sp3 hybridized orbitals of carbon in a closed-packed oxygen sublattice.

cond-mat.mtrl-sci↗

arXiv2023

Non-Fermi-Liquid Behavior of Superconducting SnH$_4$

We studied chemical interaction of Sn with H$_2$ by X-ray diffraction methods at pressures of 180-210 GPa. A previously unknown tetrahydride SnH$_4$ with a cubic structure (${fcc}$) exhibiting superconducting properties below ${T}$$_C$ = 72 K was obtained; the formation of a high molecular ${C2/m}$-SnH$_{14}$ superhydride and several lower hydrides, ${fcc}$ SnH$_2$ and ${C2}$-Sn$_{12}$H$_{18}$, was also detected. The temperature dependence of critical current density ${J}$$_C$(T) in SnH$_4$ yields the superconducting gap 2$\Delta$(0) = 23 meV at 180 GPa. SnH$_4$ has unusual behavior in strong magnetic fields: ${B,T}$-linear dependences of magnetoresistance and the upper critical magnetic field ${B}$$_{C2}$(T) $\propto$ (${T}$$_C$ - ${T}$). The latter contradicts the Wertheimer-Helfand-Hohenberg model developed for conventional superconductors. Along with this, the temperature dependence of electrical resistance of ${fcc}$ SnH$_4$ in non-superconducting state exhibits a deviation from what is expected for phonon-mediated scattering described by the Bloch-Gr\"uneisen model, and is beyond the framework of the Fermi liquid theory. Such anomalies occur for many superhydrides, making them much closer to cuprates than previously believed.

cond-mat.supr-con↗

arXiv2023

Structural evolution of iodine on approach to the monatomic state

We applied single-crystal X-ray diffraction and Raman spectroscopy in a diamond anvil cell up to 36 GPa and first principles theoretical calculations to study the molecular dissociation of solid iodine at high pressure. Unlike previously reported, we find that the familiar Cmce molecular phase transforms to a Cmc21 molecular structure at 16 GPa, and then to an incommensurate dynamically disordered Fmmm(00{\gamma})s00 structure at 20 GPa, which can be viewed as a stepwise formation of polymeric zigzag chains of three iodine atoms following by the formation of the dynamically dissociated, incommensurately modulated i-Fmmm phase, and the truly monatomic Immm phase at higher pressures.

cond-mat.mtrl-sci↗

arXiv2021

Structure and vibrational properties of methane up to 71 GPa

Single-crystal synchrotron X-ray diffraction, Raman spectroscopy, and first principles calculations have been used to identify the structure of the high-pressure (HP) phase of molecular methane above 20 GPa up to 71 GPa. The structure of HP phase is trigonal R3, which can be represented as a distortion of the cubic phase B, previously documented at 7-15 GPa and confirmed here. The positions of hydrogen atoms in HP phase have been 19 obtained from first principles calculations. The molecules occupy four different crystallographic sites in phases B and eleven sites in the HP phase, which result in splitting of molecular stretching modes detected in Raman spectroscopy and assigned here based on 22 a good agreement with the Raman spectra calculated from the first principles.

cond-mat.mtrl-sci↗

arXiv2021

Synthesis and structure of carbon doped H3S compounds at high pressure

Understanding of recently reported putative close-to-room-temperature superconductivity in C-S-H compounds at 267 GPa demands reproducible synthesis protocol as well as knowledge of its structure and composition. We synthesized C-S-H compounds with various carbon composition at high pressures from elemental C and methane CH4, sulfur S, and molecular hydrogen H2. Here we focus on compounds synthesized using methane as these allow a straightforward determination of their structure and composition by combining single-crystal X-ray diffraction (XRD) and Raman spectroscopy. We applied a two-stage synthesis of ((CH4)x(H2S)(1-x))2H2 compounds by first reacting sulfur and mixed methane-hydrogen fluids and forming CH4 doped H2S crystals at 0.5-3 GPa, and then by growing single crystals of the desired hydrogen rich compound. Raman spectroscopy applied to this material shows the presence of the CH4 molecules incorporated into the lattice and allows to determine the CH4 content, while single-crystal X-ray diffraction results suggest that the methane molecules substitute H2S ones. The structural behavior of these compounds is very similar to the previously investigated methane free compounds demonstrating a transition from Al2Cu type I4/mcm structure to a modulated structure at 20-30 GPa and back to the same basic structure in an extended modification with greatly modified Raman spectra. This latter phase demonstrates a distortion into Pnma structure at 132-159 GPa and then transforms into a common Im-3m H3S phase at higher pressures, however, no structural anomaly is detected near 220 GPa, where a sharp upturn in Tc has been reported.

cond-mat.mtrl-sci↗

arXiv2021

Thermodynamic and electronic properties of ReN$_2$ polymorphs at high-pressure

High pressure synthesis of rhenium nitride pernitride ReN$_2$ with crystal structure unusual for transition metal dinitrides and high values of hardness and bulk modulus attracted significant attention to this system. We investigate the thermodynamic and electronic properties of the P2$_1$/c phase of ReN$_2$ and compare them with two other polytypes, C2/m and P4/mbm phases suggested in the literature. Our calculations of the formation enthalpy at zero temperature show that the former phase is the most stable of the three up to pressure p=170 GPa, followed by the stabilization of the P4/mbm phase at higher pressure. The theoretical prediction is confirmed by diamond anvil cell synthesis of the P4/mbm ReN$_2$ at $\approx$175 GPa. Considering the effects of finite temperature in the quasi-harmonic approximation at p=100 GPa we demonstrate that the P2$_1$/c phase has the lowest free energy of formation at least up to 1000 K. Our analysis of the pressure dependence of the electronic structure of the rhenium nitride pernitride shows a presence of two electronic topological transitions around 18 GPa, when the Fermi surface changes its topology due to an appearance of a new electron pocket at the high-symmetry Y$_2$ point of the Brillouin zone while the disruption of a neck takes place slightly off from the $\Gamma$-A line.

cond-mat.mtrl-sci↗

arXiv2021

High-Pressure Na3(N2)4, Ca3(N2)4, Sr3(N2)4, and Ba(N2)3 Featuring Nitrogen Dimers with Non-Integer Charges and Anion-Driven Metallicity

Charged nitrogen dimers are ubiquitous in high-pressure binary metal-nitrogen systems. They are known to possess integer formal charges x varying from one through four. Here, we present the investigation of the binary alkali- and alkaline earth metal-nitrogen systems, Na-N, Ca-N, Sr-N, Ba-N to 70 GPa. We report on compounds-Na3(N2)4, Ca3(N2)4, Sr3(N2)4, and Ba(N2)3-featuring charged nitrogen dimers with paradigm-breaking non-integer charges, x = 0.67, 0.75 and 1.5. The metallic nature of all four compounds is deduced from ab initio calculations. The conduction electrons occupy the pi* antibonding orbitals of the charged nitrogen dimers that results in anion-driven metallicity. Delocalization of these electrons over the pi* antibonding states enables the non-integer electron count of the dinitrogen species. Anion-driven metallicity is expected to be found among a variety of compounds with homoatomic anions (e.g., polynitrides, carbides, and oxides), with the conduction electrons playing a decisive role in their properties.

cond-mat.mtrl-sci↗

arXiv2020

Structure and composition of C-S-H compounds up to 143 GPa

We synthesized two C-S-H compounds from a mixture of carbon and sulfur in hydrogen and from sulfur in mixed methane-hydrogen fluids at 4 GPa. X-ray synchrotron single-crystal diffraction and Raman spectroscopy have been applied to these samples up to 58 and 143 GPa, respectively. Both samples show a similar Al2Cu type I4/mcm basic symmetry, while the hydrogen subsystem evolves with pressure via variously ordered molecular and extended modifications. The methane bearing sample lowers symmetry to an orthorhombic Pnma structure after laser heating to 1400 K at 143 GPa. The results suggest that superconducting C-S-H compounds are structurally different from a common Im-3m H3S.

cond-mat.supr-con↗

arXiv2020

Stabilization of hexazine rings in potassium polynitride at high pressure

Polynitrogen molecules represent the ultimate high energy-density materials as they have a huge potential chemical energy originating from their high enthalpy. However, synthesis and storage of such compounds remain a big challenge because of difficulties to find energy efficient synthetic routes and stabilization mechanisms. Compounds of metals with nitrogen represent promising candidates for realization of energetic polynitrogen compounds, which are also environmentally benign. Here we report the synthesis of polynitrogen planar N6 hexazine rings, stabilized in K2N6 compound, which was formed from K azide upon laser heating in a diamond anvil cell at high pressures in excess of 45 GPa and remains metastable down to 20 GPa. Synchrotron X-ray diffraction and Raman spectroscopy are used to identify this material, also exhibiting metallic luster, being all consistent with theoretically predicted structural, vibrational and electronic properties. The documented here N6 hexazine rings represent new highly energetic polynitrogens, which have a potential for future recovery and utilization.

cond-mat.mtrl-sci↗

arXiv2020

High-pressure synthesis of Dirac materials: layered van der Waals bonded BeN$_4$ polymorph

High pressure chemistry is known to inspire the creation of unexpected new classes of compounds with exceptional properties. Here we report the synthesis at ~90 GPa of novel beryllium polynitrides, monoclinic and triclinic BeN4. The triclinic phase, upon decompression to ambient conditions, transforms into a compound with atomic-thick BeN4 layers interconnected via weak van der Waals bonds consisting of polyacetylene-like nitrogen chains with conjugated {\pi}-systems and Be atoms in square-planar coordination. Theoretical calculations for a single BeN4 layer show that its electronic lattice is described by a slightly distorted honeycomb structure reminiscent of the graphene lattice and the presence of Dirac points in the electronic band structure at the Fermi level. The BeN4 layer, i.e. beryllonitrene, represents a qualitatively new class of 2D materials that can be built of a metal atom and polymeric nitrogen chains and host anisotropic Dirac fermions.

cond-mat.mtrl-sci↗

arXiv2020

Novel rhenium carbides at 200 GPa

Laser heating of rhenium in a diamond anvil cell to 3000 K at about 200 GPa results in formation of two previously unknown rhenium carbides, hexagonal WC-type structured ReC and orthorhombic TiSi2-type structured ReC2. The Re-C slid solution formed at multimegabar pressure has the carbon content of ca. 20 at%. Unexpectedly long C-C distances (ca. 1.76-1.85 A) in 'graphene-like' carbon nets in the structure of ReC2 cannot be explained by a simple covalent bonding between carbon atoms and suggest that at very high pressures the mechanism of interaction between carbon atoms in inorganic compounds may be different from that considered so far.

cond-mat.mtrl-sci↗