arXiv subjects

Jesse S. Smith

Publications and source records attributed to Jesse S. Smith.

18 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, $tζ$-N$_2$, is a polytype of monoclinic $C2/c$ $ζ$-N$_2$, characterized by a tripled $c$ axis and 96 atoms per unit cell. The second, $ξ$-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 $ζ$-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 $tζ$-N$_2$ phase likely corresponds to the previously reported $κ$-N$_2$ phase.

cond-mat.mtrl-sci↗

arXiv2026

Ambient-pressure 151-K superconductivity in HgBa2Ca2Cu3O8+δ via pressure quench

Superconductivity has been a vigorously researched topic since its discovery in 1911. Raising the superconducting transition temperature (Tc) has been the main driving force behind such long-sustained efforts due to its potential for impacting humanity and the fundamental knowledge gained from understanding this macroscopic coherent quantum state at high temperatures. The successful development of high-Tc superconductivity will make possible extraordinarily efficient generation, delivery, and utilization of energy, and could also enable the development of controlled fusion while impacting other burgeoning fields like quantum computation and quantum electronics. However, progress has been hindered by a longstanding plateau in the record ambient-pressure Tc, unchanged since 1993. Subsequent significant advancements in Tc have been achieved only under high pressures, preventing the realization of superconductivity's full potential. To directly address this challenge, we developed a pressure-quench protocol (PQP) to stabilize pressure-induced/-enhanced superconducting states at ambient pressure. Here we achieve a record ambient-pressure Tc of 151 K in the cuprate HgBa2Ca2Cu3O8+δ via PQP. The experimental results are further supported by synchrotron X-ray diffraction measurements and phonon and electronic structure calculations. This breakthrough opens new avenues for stabilizing and exploring ambient-pressure high-Tc superconducting states and other quantum states that have been previously only accessible under pressure, paving the way for deeper understanding and practical applications of high-Tc superconductivity and beyond.

cond-mat.supr-con↗

arXiv2026

Novel Transformations of PbTiO3 with Pressure and Temperature

We investigated the behavior of lead titanate (PbTiO3) up to 100 GPa, both at room temperature and upon laser heating, using synchrotron X ray diffraction combined with density functional theory (DFT) computations. At the high pressure temperature (PT) conditions produced in laser heated diamond anvil cells, PbTiO3 dissociates into PbO and TiO2, consistent with our DFT computations showing that decomposition becomes enthalpically favored above 65 GPa. In contrast, on room temperature compression, PbTiO3 persists in the tetragonal I4mcm phase up to at least 100 GPa. Laser heating produces distinct PbO phases: a compressed form of alpha PbO and a previously unreported delta PbO polymorph, both of which transform to beta PbO on decompression. The calculations predict that alpha PbO undergoes pressure-induced band gap closure, metallizing above 70 GPa, whereas the delta and beta phases remain semiconducting with a band gap above 1 eV even at megabar pressures. The experimental and confirming theoretical results reveal an unanticipated dimension of the behavior of PbTiO3, showing that distinct equilibrium and metastable phases can be stabilized along different PT synthesis paths.

cond-mat.mtrl-sci↗

arXiv2024

Low-symmetry polymorph of GaP upends bonding paradigms of metallic high-pressure III-V compounds

The pressure-induced polymorphism of binary octect compounds has long been considered a settled problem although the possible atomic disordering of some phases remains a puzzling observation. Taking GaP as a case study, we conclude, through x-ray microdiffraction and first-principles calculations, that its high-pressure phase II (previously reported as being disordered) adopts in fact an ordered base-centered monoclinic structure previously unknown in this class of compounds. The formation of layered patterns with variable degrees of interlayer dimerization, as observed in GaP, marks a paradigm shift of our understanding of ordering in octect high-pressure phases which calls for a more extensive re-examination. A rich polymorphism with fine tuning of chemical and physical properties can be envisioned.

cond-mat.mtrl-sci↗

arXiv2024

Phase Boundaries, Isotope Effect and Superconductivity of Lithium Under Hydrostatic Conditions

We present theoretical and experimental studies of superconductivity and low temperature structural phase boundaries in lithium. We mapped the structural phase diagram of 6Li and 7Li under hydrostatic conditions between 5 top 55GPa and within the temperature range of 15 to 75K, observing the FCC-hR1-cI16 phase transitions. 6Li and 7Li show some differences at the structural boundaries, with a potential shift of the phase boundaries of 6Li to lower pressures. Density functional theory calculations and topological analysis of the electron density elucidates the superconducting properties and interatomic interactions within these phases of lithium.

cond-mat.supr-con↗

arXiv2023

Signatures of pressure-enhanced helimagnetic order in van der Waals multiferroic NiI$_2$

The van der Waals (vdW) type-II multiferroic NiI$_2$ has emerged as a candidate for exploring non-collinear magnetism and magnetoelectric effects in the 2D limit. Frustrated intralayer exchange interactions on a triangular lattice result in a helimagnetic ground state, with spin-induced improper ferroelectricity stabilized by the interlayer interactions. Here we investigate the magnetic and structural phase transitions in bulk NiI$_2$, using high-pressure Raman spectroscopy, optical linear dichroism, and x-ray diffraction. We obtain evidence for a significant pressure enhancement of the antiferromagnetic and helimagnetic transition temperatures, at rates of $\sim15.3/14.4$ K/GPa, respectively. These enhancements are attributed to a cooperative effect of pressure-enhanced interlayer and third-nearest-neighbor intralayer exchange. These results reveal a general path for obtaining high-temperature type-II multiferroicity via high pressures in vdW materials.

cond-mat.mtrl-sci↗

arXiv2023

Effects of Pressure on the Electronic and Magnetic Properties of Bulk NiI$_{2}$

Transition metal dihalides have recently garnered interest in the context of two-dimensional van der Waals magnets as their underlying geometrically frustrated triangular lattice leads to interesting competing exchange interactions. In particular, NiI$_{2}$ is a magnetic semiconductor that has been long known for its exotic helimagnetism in the bulk. Recent experiments have shown that the helimagnetic state survives down to the monolayer limit with a layer-dependent magnetic transition temperature that suggests a relevant role of the interlayer coupling. Here, we explore the effects of hydrostatic pressure as a means to enhance this interlayer exchange and ultimately tune the electronic and magnetic response of NiI$_{2}$. We study first the evolution of the structural parameters as a function of external pressure using first-principles calculations combined with x-ray diffraction measurements. We then examine the evolution of the electronic structure and magnetic exchange interactions via first-principles calculations and Monte Carlo simulations. We find that the leading interlayer coupling is an antiferromagnetic second-nearest neighbor interaction that increases monotonically with pressure. The ratio between isotropic third- and first-nearest neighbor intralayer exchanges, which controls the magnetic frustration and determines the magnetic propagation vector $\mathbf{q}$ of the helimagnetic ground state, is also enhanced by pressure. As a consequence, our Monte Carlo simulations show a monotonic increase in the magnetic transition temperature, indicating that pressure is an effective means to tune the magnetic response of NiI$_{2}$.

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↗

arXiv2022

Ambient temperature pressure driven alkane dehydrogenation by palladium metal

Dehydrogenation of alkanes is of increasing importance in fulfilling global demand for olefins and offers a potential source of carbon-neutral hydrogen as a co-product. Currently commercial dehydrogenation processes occur at high-temperatures (500-900$^\circ$C) which is energy intensive and results in side reactions and rapid coking of the catalysts. In addition the hydrogen produced is often burned to maintain temperature and to inhibit the back reaction. Here we demonstrate pressure as a parameter to enable novel chemical catalytic processes and demonstrate ambient-temperature dehydrogenation of alkanes by palladium at 50-100 MPa pressures, with both hydrogen gas and olefins recovered on decompression. This reaction follows a fundamentally different path to current commercial high-temperature low-pressure dehydrogenation processes with the palladium catalyst reversibly forming a hydride intermediate.

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

Pressure-induced insulator-metal transition in two-dimensional Mott insulator NiPS3

The pressure-induced insulator to metal transition (IMT) of layered magnetic nickel phosphorous tri-sulfide NiPS3 was studied in-situ under quasi-uniaxial conditions by means of electrical resistance (R) and X-ray diffraction (XRD) measurements. This sluggish transition is shown to occur at 35 GPa. Transport measurements show no evidence of superconductivity to the lowest measured temperature (~ 2 K). The structure results presented here differ from earlier in-situ work that subjected the sample to a different pressure state, suggesting that in NiPS3 the phase stability fields are highly dependent on strain. It is suggested that careful control of the strain is essential when studying the electronic and magnetic properties of layered van der Waals solids.

cond-mat.str-el↗

arXiv2021

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 π-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↗

arXiv2021

Implications of an improved water equation of state for water-rich planets

Water (H$_{2}$O), in all forms, is an important constituent in planetary bodies, controlling habitability and influencing geological activity. Under conditions found in the interior of many planets, as the pressure increases, the H-bonds in water gradually weaken and are replaced by ionic bonds. Recent experimental measurements of the water equation of state (EOS) showed both a new phase of H-bonded water ice, ice-VII$_t$, and a relatively low transition pressure just above 30 GPa to ionic bonded ice-X, which has a bulk modulus 2.5 times larger. The higher bulk modulus of ice-X produces larger planets for a given mass, thereby either reducing the atmospheric contribution to the volume of many exoplanets or limiting their water content. We investigate the impact of the new EOS measurements on the planetary mass-radius relation and interior structure for water-rich planets. We find that the change in the planet mass-radius relation caused by the systematic differences between previous and new experimental EOS measurements are comparable to the observational uncertainties in some planet sizes -- an issue that will become more important as observations continue to improve.

astro-ph.EP↗

arXiv2019

Evidence for a pressure-induced phase transition of few-layer graphene to 2D diamond

We unveil the diamondization mechanism of few-layer graphene compressed in the presence of water, providing robust evidence for the pressure-induced formation of 2D diamond. High-pressure Raman spectroscopy provides evidence of a phase transition occurring in the range of 4-7 GPa for 5-layer graphene and graphite. The pressure-induced phase is partially transparent and indents the silicon substrate. Our combined theoretical and experimental results indicate a gradual top-bottom diamondization mechanism, consistent with the formation of diamondene, a 2D ferromagnetic semiconductor. High-pressure x-ray diffraction on graphene indicates the formation of hexagonal diamond, consistent with the bulk limit of eclipsed-conformed diamondene.

cond-mat.mtrl-sci↗

arXiv2019

Bond strengthening in dense H2O and implications to planetary composition

H2O is an important constituent in planetary bodies, controlling habitability and, in geologically-active bodies, plate tectonics. At pressures within the interior of many planets, the H-bonds in H2O collapse into stronger, ionic bonds. Here we present agreement between X-ray diffraction and Raman spectroscopy for the transition from ice-VII to ice-X occurring at a pressure of approximately 30.9 GPa by means of combining grain normalizing heat treatment via direct laser heating with static compression. This is evidenced by the emergence of the characteristic Raman mode of cuprite-like ice-X and an abrupt 2.5-fold increase in bulk modulus, implying a significant increase in bond strength. This is preceded by a transition from cubic ice-VII to a structure of tetragonal symmetry, ice-VIIt at 5.1 GPa. Our results significantly shift the mass/radius relationship of water-rich planets and define a high-pressure limit for release of chemically-bound water within the Earth, making the deep mantle a potential long-term reservoir of ancient water.

cond-mat.mtrl-sci↗

arXiv2018

Post-aragonite phases of CaCO$_{3}$ at lower mantle pressures

The stability, structure and properties of carbonate minerals at lower mantle conditions has significant impact on our understanding of the global carbon cycle and the composition of the interior of the Earth. In recent years, there has been significant interest in the behavior of carbonates at lower mantle conditions, specifically in their carbon hybridization, which has relevance for the storage of carbon within the deep mantle. Using high-pressure synchrotron X-ray diffraction in a diamond anvil cell coupled with direct laser heating of CaCO$_{3}$ using a CO$_{2}$ laser, we identify a crystalline phase of the material above 40 GPa $-$ corresponding to a lower mantle depth of around 1,000 km $-$ which has first been predicted by \textit{ab initio} structure predictions. The observed $sp^{2}$ carbon hybridized species at 40 GPa is monoclinic with $P2_{1}/c$ symmetry and is stable up to 50 GPa, above which it transforms into a structure which cannot be indexed by existing known phases. A combination of \textit{ab initio} random structure search (AIRSS) and quasi-harmonic approximation (QHA) calculations are used to re-explore the relative phase stabilities of the rich phase diagram of CaCO$_{3}$. Nudged elastic band (NEB) calculations are used to investigate the reaction mechanisms between relevant crystal phases of CaCO$_{3}$ and we postulate that the mineral is capable of undergoing $sp^{2}$-$sp^{3}$ hybridization change purely in the $P2_{1}/c$ structure $-$ forgoing the accepted post-aragonite $Pmmn$ structure.

cond-mat.mtrl-sci↗

arXiv2016

Enhanced Structural Stability and Photo Responsiveness of CH3NH3SnI3 Perovskite via Pressure-Induced Amorphization and Recrystallization

An organic-inorganic halide perovskite of CH3NH3SnI3 with significantly improved structural stability is obtained via pressure-induced amorphization and recrystallization. In situ high-pressure resistance measurements reveal an increased electrical conductivity by 300% in the pressure-treated perovskite. Photocurrent measurements also reveal a substantial enhancement in visible-light responsiveness. The mechanism underlying the enhanced properties is demonstrated to be associated with the improved structural stability.

cond-mat.mtrl-sci↗

arXiv2015

Exotic stable calcium carbides: theory and experiment

It is well known that pressure causes profound changes in the properties of atoms and chemical bonding, leading to the formation of many unusual materials. Here we systematically explore all stable calcium carbides at pressures from ambient to 100 GPa using variable-composition evolutionary structure predictions. We find that Ca5C2, Ca2C, Ca3C2, CaC, Ca2C3, and CaC2 have stability fields on the phase diagram. Among these, Ca2C and Ca2C3 are successfully synthesized for the first time via high-pressure experiments with excellent structural correspondence to theoretical predictions. Of particular significance are the base-centered monoclinic phase (space group C2/m) of Ca2C, a quasi-two-dimensional metal with layers of negatively charged calcium atoms, and the primitive monoclinic phase (space group P21/c) of CaC with zigzag C4 groups. Interestingly, strong interstitial charge localization is found in the structure of R-3m-Ca5C2 with semimetallic behaviour.

cond-mat.mtrl-sci↗