Structure and thermodynamic stability of carbon clathrates: A Monte Carlo study

Clathrates are strong, low density, fully sp³ structures that have been found for several elements of the IV group. Carbon clathrates however are, as of now, hypothetical materials. Ab initio calculations at $T=0K$ predict carbon clathrates to be metastable with remarkable mechanical and electronic properties. Here we study the behavior and structural stability of the type I C₄₆ carbon clathrates up to high temperature and pressure by means of Monte Carlo simulations based on an accurate model for the interatomic interactions. We find that the clathrate structure remains mechanically stable up to melting and we report the equilibrium structural parameters, thermal expansion, and equation of state.     

Pressure Study on New Superconducting Germanium Clathrates

We investigate the low temperature properties of the recently discovered clathrates Ba 6 Ge 25 and Na 2 Ba 4 Ge 25 by tuning both materials with hydrostatic pressure. At ambient pressure, Ba 6 Ge 25 undergoes a two-step structural phase transition between 230 K and 180 K from metallic behavior to a high-resistivity state. A superconducting transition occurs at T_{C}\approx 0.24\,\hbox{K} out of the resulting bad metal ( \rho_{0}\approx 1.5\,\hbox{m}\Omega\;\hbox{cm} ). With increasing pressure, the structural phase transition is shifted to lower temperature but T C increases drastically. T C reaches a maximum value of 3.85 K at the critical pressure p_{C}\approx 2.8\,\hbox{GPa} , where the structural distortion is completely suppressed and the system exhibits metallic behavior. On replacing 1/3 of the Ba atoms with Na (Na 2 Ba 4 Ge 25 ), no structural transformation is observed below room temperature, and the superconducting transition temperature is higher (T_{C}(p = 0) \approx 1.05\,\hbox{K}) than in the undoped case at ambient pressure but decreases slightly with increasing pressure.     

Structural and electronic properties of type-I and type-VIII Ba8Ga16Sn30 clathrates under compression

The total energy and electronic structures for type-I (β phase) and type-VIII (α phase) Ba₈Ga₁₆Sn₃₀ clathrates under hydrostatic pressure have been investigated using density functional theory (DFT) calculations. It was found that the type-VIII phase is more stable than the type-I one at ambient conditions and that β→α phase transition can not occur under hydrostatic pressure. The band structures show that the type-I and type-VIII Ba₈Ga₁₆Sn₃₀ are indirect semiconductors with band gaps of 0.24 eV and 0.19 eV, respectively. The results suggested that type-I clathrate Ba₈Ga₁₆Sn₃₀ has a larger value of the thermoelectric (TE) power than that of type-VIII clathrate. We found that pressure tuning changes the k-point of conduction band minimum (CBM) in the Brillouin zone for β-phase, but it is not the case for α-phase. Furthermore, the results show that the pressure can change the interaction between guest atoms and the host lattice, and consequently results in the decrease of the band gap of β-phase and the increase of the band gap of α-phase, indicating that the pressure effect can play an important role in the magnitude of the TE power.     

Characterization of Salting-Out Processes during CO2-Clathrate Formation Using Raman Spectroscopy: Planetological Application

Clathrate hydrates are particular solids that planetologists study in detail because those solids may be present in several bodies of the solar system, such as Mars, comets, and the icy satellites. The solids are formed by solid H₂O, like common water ice, but adopt open structures with cavities containing gas molecules. Clathrate hydrates are usually stable at relatively low temperature and high pressure, which are the typical conditions present inside these planetary objects. Their interest for astrobiology is that they represent potential sources of liquid water and gases when they decompose. The present work is focused on the crystallization of clathrates in Europa's (icy satellite of Jupiter) interior conditions. We postulate that clathrate hydrates may play an important role in its crust mineralogy and that it can explain some features of the satellite's surface due to their formation/destabilization. An in situ kinetic study by Raman Spectroscopy of the clathrate formation from salty solutions was performed in our laboratory. The chemical composition that we used mimics those obtained from Europa's surface during the Galileo mission. An effect of the salting-out process in the solution was monitored through the clathrate formational path. Our results demonstrate that this process may have geological consequences on Europa and confirm the suitability of Raman spectroscopy for planetary detection of clathrate hydrates and other ices.     

Thermal conductivity of ice and ice clathrate

We present the results of an investigation of the thermal conductivity, k, of ice and an ice clathrate (1,3-dioxolane). It is observed that k for the clathrate depends upon the cooling rate during solidification and the temperature dependence of k differs from that of amorphous materials unless the cooling rate is rapid. A consistent picture of thermal conduction in ice and clathrates is given on the basis of tunnelling states arising from proton disorder.     

Structural principles and amorphouslike thermal conductivity of Na-doped Si clathrates

The postulated low thermal conductivity and the possibility of altering the electronic conductivity of metal-doped clathrates with semiconducting host elements have stimulated great interest in exploring these compounds as promising thermoelectric materials. The electronic and thermal properties of the prototypical Na xSi (46) system are studied in detail here. It is shown that, despite the fact that the Na/Si clathrate is metallic, its thermal conductivity resembles that of an amorphous solid. A theoretical model is developed to rationalize the structural stability of the peculiar structural topology, and a general scheme for rational design of high efficiency thermoelectric materials is presented.     

A New Class of Low Compressibility Materials: Clathrates of Silicon and Related Materials

We discuss the high pressure properties of different silicon clathrate structures that we have investigated by means of X-ray diffraction and ab initio calculations. Compressibility, transition pressures or phase transformations are interpreted as a function of the nature of the guest atom intercalation. The compressibility of the clathrate structure is in all cases close to that of silicon diamond whereas transition pressures or the high pressure phases are extremely depending on the nature of the guest atom. We address the implications for obtaining a metallic material as hard as diamond.     

High pressure effect on structural and mechanical properties of some LnO (Ln=Sm, Eu, Yb) compounds

The structural and mechanical properties of LnO (Ln=Sm, Eu, Yb) compounds have been investigated using a modified interionic potential theory, which includes the effect of Coulomb screening. We predicted a structural phase transition from NaCl (B₁)- to CsCl (B₂)-type structure and elastic properties in LnO compounds at very high pressure. The anomalous properties of these compounds have been correlated in terms of the hybridisation of f-electrons of the rare earth ion with conduction band and strong mixing of f-states of lanthanides with the p-orbital of neighbouring chalcogen ion. For EuO, the calculated transition pressure, bulk modulus and lattice parameter are close to the experimental data. The nature of bonds between the ions is predicted by simulating the ion-ion (Ln-Ln and Ln-O) distances at high pressure. The second order elastic constants along with shear modulus and Young's modulus, elastic anisotropy and Poisson's ratio are also presented for these oxides.     

Computational investigations of inhomogeneous elastic effects near phase transitions

Abstract

We present different approaches to computer simulations of the order-disorder phase transition in thiocyanate crystals. In these systems the order parameter is coupled to the strain by coupling of the type ?²ε. This coupling plays the dominant role in the behavior of the system below T _c. Molecular Dynamics and Monte Carlo techniques give the proper temperature dependence of the order parameter and the behavior of the fluctuations similar to that observed experimentally. The ab initio calculations allow us to render properly the structural properties of crystals like KSCN and additionally can become the basis for more realistic phenomenological models.     

First-principles studies of structural,mechanical, electronic,optical properties and pressure-induced phase transition of CuInO2 polymorph

Using the first-principles density-functional theory within the generalized gradient approximation (GGA), we have investigated the structural, elastic, mechanical, electronic, and optical properties and phase transition of CuInO₂. Structural parameters including lattice constants and internal parameter, pressure effects and phase transition pressure were calculated. We have obtained the elastic coefficients, bulk modulus, shear modulus, Young's modulus and Poisson's ratio. We find that two phases of CuInO₂ are indirect band gap semiconductors (F–Γ and H–Γ for 3R and 2H, respectively). Optical properties, including the dielectric function, refractive index, extinction coefficient, reflectivity, absorption coefficient, loss function and optical conductivity have been obtained for radiations of up to 30 eV.     

Superconductivity of topological matters induced via pressure

By applying pressure on the topological insulator Bi₂Te₃ single crystal, superconducting phase was found without a crystal structure phase transition. The new superconducting phase is under the pressure range of 3 GPa to 6 GPa. The high pressure Hall effect measurements indicated that the superconductivity caused by bulk hole pockets. The high pressure structure investigations with synchrotron X-ray diffraction indicated that the superconducting phase is of similar structure to that of ambient phase structure with only slight change with lattice parameter and internal atomic position. The topological band structures indicate the superconducting phase under high pressure remained topologically nontrivial. The results suggested that topological superconductivity can be realized in Bi₂Te₃ due to the proximity effect between superconducting bulk states and Diractype surface states. We also discussed the possibility that the bulk state could be a topological superconductor.     

Investigation of the mobility of paraffin molecules in channel urea clathrates by nuclear magnetic resonance relaxation spectroscopy

The temperature dependence of the proton spin-lattice relaxation time (T ₁) is investigated for channel urea clathrates with paraffin molecules. The results obtained are interpreted within the reorientational model of paraffin molecules and their fragments in clathrate channels. The specific features of the dynamics of normal paraffins in urea clathrates are associated with incommensurate regions in the structure of these compounds.     

Shock wave working of high-TC superconductors

Abstract

The results of investigating the processes of explosive compaction of Y-Ba-Cu-O and Bi-Sr-Ca-Cu-O powdered ceramic high temperature superconducting materials and the shock-induced variation of their properties are presented. The possibility for obtaining metal-ceramic cylinder and spiral-shaped articles is illustrated. The shock wave loading of sintered ceramics is shown to result in degrading its superconducting properties up on R(T), which are subsequently restored by low-temperature annealing. The loss of superconducting properties is demonstrated to correlate with the X-ray lines width. In case of Bi-4334 ceramic, we have observed the improving SP-properties on susceptibility just after shocking it. The effect of the compaction pressure, initial particle size, atmosphere (air, O₂, N₂), initial temperature on material properties is studied.     

Shift of the optical absorption edge in C60 clathrate single crystals

We measured the transmission between 1.6–2.2 eV of pure C₆₀ and three clathrate single crystals containing different aliphatic guest molecules. The absorption edge in the clathrates shows a blue shift of 0.1 eV irrespective of the guest molecule, indicating that C₆₀ is electronically isolated in these compounds.     

First principles study of the structural,electronic, mechanical and superconducting properties of WX (X=C,N)

The structural, electronic, mechanical and superconducting properties of tungsten carbide (WC) and tungsten nitride (WN) are investigated using first principles calculations based on density functional theory (DFT). The computed ground state properties, such as equilibrium lattice constant and cell volume, are in good agreement with the available experimental data. A pressure induced structural phase transition is observed in both tungsten carbide and nitride, from a tungsten carbide phase (WC) to a zinc blende phase (ZB), and from a zinc blende phase (ZB) to a wurtzite phase (WZ). The electronic structure reveals that these materials are metallic at ambient conditions. The calculated elastic constants obey the Born-Huang criteria, suggesting that they are mechanically stable at normal and high pressure. Also, the superconducting transition temperature is estimated for the WC and WN in stable structures at atmospheric pressure.     

Superconductivity and the b.c.c. to A-15 transformation in Nb-Au alloys2

Nb-Au alloys near the composition Nb₃Au can be quenched from the high temperature α solid solution phase field, retaining the b.c.c. structure. We report results on their superconducting, mechanical and physical properties as a function of composition. Short low temperature anneals transform these materials to the equilibrium A-15 structure with T_c up to 11K. We report results on the superconducting and physical properties of the transformed A-15 structure materials and describe how the properties of the transformed materials are affected by annealing temperature and time.     

27Al NMR spectroscopy of minerals and related materials

We present a review of the applications of²⁷Al NMR methods to investigations of the structures of minerals, primarily alumino-silicates, and related synthetic compounds. Such materials are ubiquitous in the earth and other terrestrial planets. Because of their diverse structures and compositions, they also provide examples of many situations in which²⁷Al NMR spectroscopy can provide useful information. Thus, they serve well as model compounds for synthetic crystalline and amorphous materials and usefully illustrate the applications of many techniques. The advent of high-field superconducting magnets (H ₀>9 T) has made application of²⁷Al NMR to solids much more effective than it was previously, and we focus primarily on these recent applications but also discuss older, single-crystal data.²⁷Al NMR methods can be used for many purposes in investigations of solids. Here we emphasize the following. 1) Determination of the Al coordination number and the polymerization of tetrahedrally coordinated Al. 2) Determination of tetrahedral Al/octahedral Al ratios. 3) Investigation of tetrahedral Al, Si order/disorder in, especially, framework-structure alumino-silicate phases. 4) Investigation of the static structural changes and dynamical behavior of crystals undergoing structural phase transitions. 5) Investigation of the local symmetry of Al-sites through the quadrupole coupling constant and asymmetry parameter.     

Structure and magnetism of Coa(1−x)MnaxGeb epitaxial films

The structural and magnetic phase diagrams of Co_a(1−x)Mn_axGe_b epitaxial films near the composition of Heusler alloy Co₂MnGe have been studied using combinatorial molecular beam epitaxy techniques. Epitaxial growth on Ge (1 1 1) has been stabilized over nearly the entire composition range of the ternary system. Epitaxial constraints play an important role for the small number of observed structural phases. The variety of high-temperature magnetic properties, and the structural and chemical compatibilities with group IV elements make the ternary system promising for the science and applications of spintronics.     

Comparative Study on Pressure-Induced Structural Changes between C 6 O 2 I 4 and C 6 I 6

We have investigated the pressure effects on the structural properties of C 6 O 2 I 4 up to 39 GPa by powder x-ray diffraction measurements, which were compared with those of C 6 I 6 . The diffraction patterns of C 6 O 2 I 4 indicated a phase transition starting at 26.8 GPa. The mixed state of the low- and high-pressure phases continued up to 39 GPa well above an insulator-to-metal transition pressure of 33 GPa. The C 6 O 2 I 4 molecule remains planar structure in the low-pressure phase below 26.8 GPa in contrast to the non-planar molecular structure of C 6 I 6 at ambient and high pressures.     

Thermoelectric properties of tin clathrates under hydrostatic pressure

We report the temperature dependence of electrical resistance (R) and thermopower (S) of clathrate Cs₈Sn₄₄ under high pressure up to 1.2 GPa. We observe a reversible gap widening, prominent relaxation effect of R, irreversible increase of |S| under high pressure. We also find that the power factor S²σ (σ: electrical conductivity) reaches a maximum at pressure of 0.3 GPa. Comparison of the experimental results with band structure calculations suggests that the intrinsic vacancy in the clathrate structure of Cs₈Sn₄₄ plays an important role in transport properties under high pressure. Measurements on Cs₈Zn₄Sn₄₂, a clathrate which has defects other than vacancies, are compared with Cs₈Sn₄₄. The results indicate that replacing Sn by Zn has similar effect as the intrinsic vacancy on S.