By means of first-principles methods we analyze the optical response of transparent dense sodium as a function of applied pressure. We discover an unusual kind of charge-transfer exciton that proceeds from the interstitial distribution of valence electrons repelled away from the ionic cores by the Coulomb interaction and the Pauli repulsion. The predicted absorption spectrum shows a strong anisotropy with light polarization that just at pressures above the metal-insulator transition manifests as sodium being optically transparent in one direction but reflective in the other. This result provides a key information about the crystal structure of transparent sodium, a new unconventional inorganic electride.
Sodium pentazolates NaN5 andNa2N5, new high energy density materials, are discovered during first principles crystal structure search for the compounds of varying amounts of elemental sodium and nitrogen. The pentazole anion N5- is stabilized in the condensed phase by sodium Na+ cations at pressures exceeding 20 GPa, and becomes metastable upon release of pressure. The sodium azide (NaN3) precursor is predicted to undergo a chemical transformation above 50 GPa into sodium pentazolates NaN5 and Na2N5. The calculated Raman spectrum of NaN5 is in agreement with the experimental Raman spectrum of …
Alkali metals exhibit unexpected structures and electronic behavior at high pressures. Compression of metallic sodium (Na) to 200 GPa leads to the stability of a wide-band-gap insulator with the double hexagonal hP4 structure. Post-hP4 structures remain unexplored, but they are important for addressing the question of the pressure at which Na reverts to a metal. Here we report the reentrant metallicity of Na at the very high pressure of 15.5 terapascal (TPa), predicted using first-principles structure searching simulations. Na is therefore insulating over the large pressure range of 0.2-15.5 T…
The only known compound of sodium and hydrogen is archetypal ionic NaH. Application of high pressure is known to promote states with higher atomic coordination, but extensive searches for polyhydrides with unusual stoichiometry remain unsuccessful in spite of several theoretical predictions. Here we report the first observation of formation of polyhydrides of Na (NaH3 and NaH7) above 40 GPa and 2000 K. We combined synchrotron x-ray diffraction and Raman spectroscopy in a laser heated diamond anvil cell and theoretical Ab-Initio Random Structure search, which both agree in stable structures and…
Helium is generally understood to be chemically inert and this is due to its extremely stable closed-shell electronic configuration, zero electron affinity and an unsurpassed ionization potential. It is not known to form thermodynamically stable compounds, except a few inclusion compounds. Here, using the ab initio evolutionary algorithm USPEX and subsequent high-pressure synthesis in a diamond anvil cell, we report the discovery of a thermodynamically stable compound of helium and sodium, Na2He, which has a fluorite-type structure and is stable at pressures >113 GPa. We show that the presence…
The high-pressure and high-temperature behaviors of sodium chloride (NaCl) have the fundamental and application significance to the high pressure physics and chemistry. To explore the reactivity of NaCl at high pressure and high temperature, we compressed the NaCl samples to pressures up to 85 GPa and heated them to a temperature of 1800 by using the diamond anvil cell and the double-sided laser heating technology. Our investigation of Raman spectroscopy shows that NaCl decomposes to NaCl3 with orthorhombic Pnma structure plus possible Na3Cl with tetragonal P4/mmm structure above 31 GPa. It sh…
Re-entrant melting (in which a substance's melting point starts to decrease beyond a certain pressure) is believed to be an unusual phenomenon. Among the elements, it has so far only been observed in a very limited number of species, e.g., the alkali metals. Our density functional theory calculations reveal that this behavior actually extends beyond alkali metals to include magnesium, which also undergoes re-entrant melting, though at the much higher pressure of ~300 GPa. We find that the origin of re-entrant melting is the faster softening of interatomic interactions in the liquid phase than …
First-principles molecular dynamics (FPMD) simulations are performed on 6 and 12% Na in dense liquid N. A detailed description of structural and electronic properties leading to an understanding of the effect of Na-doping on the polymerization phase transition of N is presented. Compression of the mixtures from 5 to 90 GPa shows three distinct regions of characteristic local order separated by pressures near 30 and 65 GPa. Computation of Gibbs free energies of mixing shows that these mixtures are thermodynamically stable beyond 20 and 15 GPa for 6 and 12 % Na respectively.
The application of high pressure can fundamentally modify the crystalline and electronic structures of elements as well as their chemical reactivity, which could lead to the formation of novel materials. Here, we explore the reactivity of lithium with sodium under high pressure, using a swarm structure searching techniques combined with first-principles calculations, which identify a thermodynamically stable LiNa compound adopting an orthorhombic oP8 phase at pressure above 355 GPa. The formation of LiNa may be a consequence of strong concentration of electrons transfer from the lithium and th…
Na2IrO3 (NIO) is known to be a spin-orbit (SO) driven j=1/2 pseudo-spin Mott-Hubbard (M-H) insulator. However, the microscopic origin of the pseudo-spin state and the role of local structural distortions have not been clearly understood. Using a combination of theoretical calculations and x-ray spectroscopy, we show that the energetics in the vicinity of Fermi level (EF) is governed by SO interactions, electron correlation and local octahedral distortions. Contrary to the earlier understanding, here we show that the j=3/2 and 1/2 pseudo-spin states have admixture of both t2g and eg characters …
The complex structures and electronic properties of alkali metals and their alloys provide a natural laboratory for studying the interelectronic interactions of metals under compression. A recent theoretical study (J. Phys. Chem. Lett. 2019, 10, 3006) predicted an interesting pressure-induced decomposition-recombination behavior of the Na2K compound over a pressure range of 10 - 500 GPa. However, a subsequent experiment (Phys. Rev. B 2020, 101, 224108) reported the formation of NaK rather than Na2K at pressures above 5.9 GPa. To address this discordance, we study the chemical stability of diff…
Pressure-induced insulator-to-metal transition (IMT) has been studied in the van der Waals compound iron thiophosphate (FePS3) using first-principles calculations within the periodic linear combination of atomic orbitals method with hybrid Hartree-Fock-DFT B3LYP functional. Our calculations reproduce correctly the IMT at ~15 GPa, which is accompanied by a reduction of the unit cell volume and of the vdW gap. We found from the detailed analysis of the projected density of states that the 3p states of phosphorus atoms contribute significantly at the bottom of the conduction band. As a result, th…
Hydrostatic pressure and oxygen vacancies usually have deleterious effects on ferroelectric materials because both tend to reduce their polarization. In this work we use first-principles calculations to study an important class of ferroelectric materials - LiNbO$_3$-type ferroelectrics (LiNbO$_3$ as the prototype), and find that in oxygen-deficient LiNbO$_{3-δ}$, hydrostatic pressure induces an unexpected metal-insulator transition between 8 and 9 GPa. Our calculations also find that strong polar displacements persist in both metallic and insulating oxygen-deficient LiNbO$_{3-δ}$ and the size …
Lithium and sodium decorated PHE-graphene for high capacity hydrogen storage: A DFT and GCMC study
Jiangsu Provincial Engineering Research Center of Low-Dimensional Physics and New Energy, College of Science, Nanjing University of Posts and Telecommunications（南京邮电大学理学院低维物理与新能源江苏省工程研究中心）
Transport properties of Ce$_{0.85}$F0.15SbS$_{2}$ and undoped CeOSbS$_{2}$ under high pressure were investigated experimentally and theoretically. Electrical resistivity measurements of the Ce$_{0.85}$F0.15SbS$_{2}$ single crystals were performed under various high pressures using a diamond anvil cell with boron-doped diamond electrodes. The samples showed the insulator to metal transition by applying high pressure up to 30-40 GPa. On the other hand, the undoped CeOSbS$_{2}$ showed almost same transport property with the F-doped sample under high pressure. The valence state analysis using X-ra…
Anisotropic magnetoresistance (AMR) of Cr2Ge2Te6 (CGT), a layered ferromagnetic insulator, is investigated under an applied hydrostatic pressure up to 2 GPa. The easy axis direction of the magnetization is inferred from the AMR saturation feature in the presence and absence of the applied pressure. At zero applied pressure, the easy axis is along the c-direction or perpendicular to the layer. Upon application of a hydrostatic pressure>1 GPa, the uniaxial anisotropy switches to easy-plane anisotropy which drives the equilibrium magnetization from the c-axis to the ab-plane at zero magnetic fiel…
Intrinsic magnetic topological insulators provide an ideal platform to achieve various exciting physical phenomena. However, this kind of materials and related research are still very rare. In this work, we reported the electronic and structural phase transitions in intrinsic magnetic topological insulator MnSb2Te4 driven by hydrostatic pressure. Electric transport results revealed that temperature dependent resistance showed a minimum value near short-range antiferromagnetic (AFM) ordering temperature TN', the TN' values decline with pressure, and the AFM ordering was strongly suppressed near…
Based on the Phase Hamiltonian, two types of solitons are found to exist in the crossover region between band insulator and Mott insulator in one-dimension. Both of these solitons have fractional charges but with different spins, zero and 1/2, respectively. The results are in accord with the experimental results by Kanoda et al. for TTF-Chloranil under pressure.
In-situ high pressure single crystal X-ray diffraction study reveals that the quantum material CaMn$_2$Bi$_2$ undergoes a unique plane to chain structural transition between 2 and 3 GPa, accompanied by a large volume collapse. CaMn2Bi2 displays a new structure type above 2.3 GPa, with the puckered Mn honeycomb lattice of the trigonal ambient-pressure structure converting to one-dimensional (1D) zigzag chains in the high-pressure monoclinic structure. Single crystal measurements reveal that the pressure-induced structural transformation is accompanied by a dramatic two order of magnitude drop o…
Silicon telluride (Si2Te3) is a two-dimensional semiconductor with unique structural properties due to the size contrast between Si and Te atoms. A recent experiment shows that the material turns metallic under hydrostatic pressure, while the lattice structure of the metallic phase remains to be identified. In this paper, we propose two metallic phases, M1 and M2, of Si2Te3 using the evolution algorithm and first-principles density functional theory (DFT) calculations. Unlike the presence of Si-Si dimers in the semiconducting (SC) phase, both M1 and M2 phases have individual Si atoms, which pl…
Recent developments in higher-order topological phases have elucidated on the relationship between nontrivial multipole moments in the bulk and the emergence of fractionally quantized charges at the boundary. Here, we put on the table a proposal of the three-dimensional octupole insulator with fractionally quantized corner charges $\pm e/8$: sodium chloride, commonly known as table salt. The fractional quantization of the corner charge is unaffected by the quantum fluctuation of the electric charge per ion, as we demonstrate explicitly with ab initio calculations. We further show that the elec…
Crystal structures of $\textrm{CLi}_4$ compounds are explored through \emph{ab} \emph{initio} evolutionary methodology. Phase transition from metal to semimetal and semiconductor, and eventually to insulator with increasing pressure are revealed under pressure. Pressure-induced evolution of anti-metallization has been described quantitatively by Fermi Surface Filling Ratio and electron energy band gap using \emph{ab} \emph{initio} \emph{GW} calculations. Anti-metallization is attributed to the hybrid valence electrons and their repulsion by core electrons into the lattice interstices. Very wea…
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 depen…
Attractive negative-$U$ interactions between electrons facilitated by strong electron-phonon interaction are common in highly polarizable and disordered materials such as amorphous chalcogenides, but there is no direct evidence for them in large-band-gap insulators. Here we report how such negative-$U$ centers are responsible for widespread insulator-to-metal transitions in amorphous HfO$_2$ and Al$_2$O$_3$ thin films with a 10$^9$-fold resistance drop. Triggered by a static hydraulic pressure or a 0.1 ps impulse of magnetic pressure, the transition can proceed at such low pressure that there …
We study the influence of external pressure on the electronic and magnetic structure of EuMnO3 from first-principles calculations. We find a pressure-induced insulator-metal transition at which the magnetic order changes from A-type antiferromagnetic to ferromagnetic with a strong interplay with Jahn-Teller distortions. In addition, we find that the non-centrosymmetric E*-type antiferromagnetic order can become nearly degenerate with the ferromagnetic ground state in the high-pressure metallic state. This situation can be exploited to promote a magnetically-driven realization of a non-centrosy…
We report the electronic properties of the NdNiO3, prepared at the ambient oxygen pressure condition. The metal-insulator transition temperature is observed at 192 K, but the low temperature state is found to be less insulating compared to the NdNiO3 prepared at high oxygen pressure. The electric resistivity, Seebeck coefficient and thermal conductivity of the compound show large hysteresis below the metal-insulator transition. The large value of the effective mass (m* ~ 8me) in the metallic state indicate the narrow character of the 3d band. The electric conduction at low temperatures (T = 2 …
Pressure-induced metal-insulator and spin-state transition in low-valence layered nickelates
从头计算预测，在零温度下的金属-绝缘体转变发生在La $_4$ Ni $_3$ O $_8$在中等压力下作为压力诱导的自旋态转变的结果。已经观察到在105 K在环境压力下从低温高自旋状态到高温低自旋状态的自旋状态转变随着压力的施加而向较低温度转移。从我们的计算中，我们发现，较小的晶胞体积有利于金属低自旋态，它变得更稳定，在5 GPa。类似的物理现象应该发生在相关化合物La $_3$ Ni $_2$ O $_6$中，但在不同的能量尺度上，这可能解释了为什么在这种材料中没有观察到跃迁。
A complex interplay of different energy scales involving Coulomb repulsion, spin-orbit coupling and Hund's coupling energy in two-dimensional (2D) van der Waals (vdW) material produces novel emerging physical state. For instance, ferromagnetism in vdW charge transfer insulator CrGeTe$_3$, that provides a promising platform to simultaneously manipulate the magnetic and electrical properties for potential device implementation using few layers thick materials. Here, we show a continuous tuning of magnetic and electrical properties of CrGeTe$_3$ single crystal using pressure. With application of …
