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Chemical modifications such as intercalation can be used to modify surface properties or to further functionalize the surface states of topological insulators (TIs). Using ambient pressure x-ray photoelectron spectroscopy, we report copper migration in C u x B i 2 S e 3 , which occurs on a timescale of hours to days after initial surface cleaving. The increase in near-surface copper proceeds along with the oxidation of the sample surface and large changes in the selenium content. These complex changes are further modeled with core-level spectroscopy simulations, which suggest a composition gradient near the surface which develops with oxygen exposure. Our results shed light on a new phenomenon that must be considered for intercalated TIs—and intercalated materials in general—that surface chemical composition can change when specimens are exposed to ambient conditions.

A new type-I clathrate, Ba8Cu14Ge6P26, was synthesized by solid-state methods as a polycrystalline powder and grown as a cm-sized single crystal via the vertical Bridgman method. Single-crystal and powder X-ray diffraction show that Ba8Cu14Ge6P26 crystallizes in the cubic space group Pm3n (no. 223). Ba8Cu14Ge6P26 is the first representative of anionic clathrates whose framework is composed of three atom types of very different chemical natures: a transition metal, tetrel element, and pnicogen. Uniform distribution of the Cu, Ge, and P atoms over the framework sites and the absence of any superstructural or local ordering in Ba8Cu14Ge6P26 were confirmed by synchrotron X-ray diffraction, electron diffraction and high-angle annular dark field scanning transmission electron microscopy, and neutron and X-ray pair distribution function analyses. Characterization of the transport properties demonstrate that Ba8Cu14Ge6P26 is a p-type semiconductor with an intrinsically low thermal conductivity of 0.72 W m-1 K-1 at 812 K. The thermoelectric figure of merit, ZT, for a slice of the Bridgman-grown crystal of Ba8Cu14Ge6P26 approaches 0.63 at 812 K due to a high power factor of 5.62 μW cm-1 K-2. The thermoelectric efficiency of Ba8Cu14Ge6P26 is on par with the best optimized p-type Ge-based clathrates and outperforms the majority of clathrates in the 700-850 K temperature region, including all tetrel-free clathrates. Ba8Cu14Ge6P26 expands clathrate chemistry by bridging conventional tetrel-based and tetrel-free clathrates. Advanced transport properties, in combination with earth-abundant framework elements and congruent melting make Ba8Cu14Ge6P26 a strong candidate as a novel and efficient thermoelectric material.

A new type-I clathrate, Ba8Cu14Ge6P26, was synthesized by solid-state methods as a polycrystalline powder and grown as a cm-sized single crystal via the vertical Bridgman method. Single-crystal and powder X-ray diffraction show that Ba8Cu14Ge6P26 crystallizes in the cubic space group Pm3n (no. 223). Ba8Cu14Ge6P26 is the first representative of anionic clathrates whose framework is composed of three atom types of very different chemical natures: a transition metal, tetrel element, and pnicogen. Uniform distribution of the Cu, Ge, and P atoms over the framework sites and the absence of any superstructural or local ordering in Ba8Cu14Ge6P26 were confirmed by synchrotron X-ray diffraction, electron diffraction and high-angle annular dark field scanning transmission electron microscopy, and neutron and X-ray pair distribution function analyses. Characterization of the transport properties demonstrate that Ba8Cu14Ge6P26 is a p-type semiconductor with an intrinsically low thermal conductivity of 0.72 W m-1 K-1 at 812 K. The thermoelectric figure of merit, ZT, for a slice of the Bridgman-grown crystal of Ba8Cu14Ge6P26 approaches 0.63 at 812 K due to a high power factor of 5.62 μW cm-1 K-2. The thermoelectric efficiency of Ba8Cu14Ge6P26 is on par with the best optimized p-type Ge-based clathrates and outperforms the majority of clathrates in the 700-850 K temperature region, including all tetrel-free clathrates. Ba8Cu14Ge6P26 expands clathrate chemistry by bridging conventional tetrel-based and tetrel-free clathrates. Advanced transport properties, in combination with earth-abundant framework elements and congruent melting make Ba8Cu14Ge6P26 a strong candidate as a novel and efficient thermoelectric material.

Nuclear-magnetic resonance (NMR) spectra of CsCl and LaCl3 in D2O/H2O solutions were collected up to pressures of 1.9 GPa using a new NMR probe design that considerably extends the pressure range available for geochemical experiments. The longitudinal-relaxation times (T1) for 2H compare well with those reported in the previous studies of Lee et al. (1974), who examined lower pressures, and indicate that the probe functions properly. In some experiments, 133Cs and 1H NMR spectra could be taken on solutions to pressures well beyond the nominal freezing pressure of D2O or H2O to form Ice VI (near 0.9 GPa). Freezing to form the high-pressure ice is kinetically slow on an experimental time scale (minutes to hours). The data indicate that the electrolyte concentrations increase the freezing pressure of the solution. This result means that solution NMR spectra can be collected at pressures that are nearly twice the nominal freezing pressure of pure D2O or H2O. Pulsed-magnetic-field-gradient NMR methods are used to independently measure the self-diffusion coefficient of H2O in these solutions, which yields estimates of solution viscosity via the Stokes–Einstein relation. The increased viscosity accounts for the pressure variation of T1 values as rates of molecular tumbling are affected. Accounting for such changes is essential if NMR spectral line widths are used to infer pressure-enhanced rates of geochemical reactions, such as interconversion of aqueous complexes.

Nuclear spin relaxation rates of (2) H and (139) La in LaCl3 +(2) H2 O and La(ClO4 )3 +(2) H2 O solutions were determined as a function of pressure in order to demonstrate a new NMR probe designed for solution spectroscopy at geochemical pressures. The (2) H longitudinal relaxation rates (T1 ) vary linearly to 1.6 GPa, consistent with previous work at lower pressures. The (139) La T1 values vary both with solution chemistry and pressure, but converge with pressure, suggesting that the combined effects of increased viscosity and enhanced rates of ligand exchange control relaxation. This simple NMR probe design allows experiments on aqueous solutions to pressures corresponding roughly to those at the base of the Earth's continental crust.

Nuclear spin relaxation rates of (2) H and (139) La in LaCl3 +(2) H2 O and La(ClO4 )3 +(2) H2 O solutions were determined as a function of pressure in order to demonstrate a new NMR probe designed for solution spectroscopy at geochemical pressures. The (2) H longitudinal relaxation rates (T1 ) vary linearly to 1.6 GPa, consistent with previous work at lower pressures. The (139) La T1 values vary both with solution chemistry and pressure, but converge with pressure, suggesting that the combined effects of increased viscosity and enhanced rates of ligand exchange control relaxation. This simple NMR probe design allows experiments on aqueous solutions to pressures corresponding roughly to those at the base of the Earth's continental crust.

A non-magnetic piston-cylinder pressure cell is presented for solution-state NMR spectroscopy at geochemical pressures. The probe has been calibrated up to 20 kbar using in situ ruby fluorescence and allows for the measurement of pressure dependencies of a wide variety of NMR-active nuclei with as little as 10 μL of sample in a microcoil. Initial (11)B NMR spectroscopy of the H3BO3-catechol equilibria reveals a large pressure-driven exchange rate and a negative pressure-dependent activation volume, reflecting increased solvation and electrostriction upon boron-catecholate formation. The inexpensive probe design doubles the current pressure range available for solution NMR spectroscopy and is particularly important to advance the field of aqueous geochemistry.

Magnetic susceptibility, magnetization, specific heat, and electrical resistivity studies on single crystals of Ce4Pt12Sn25 reveal an antiferromagnetic transition at T(N) = 0.19 K, which develops from a paramagnetic state with a very large specific heat coefficient (C/T) of 14 J mol(-1) K(-2)-Ce just above T(N). On the basis of its crystal structure and these measurements, we argue that a weak magnetic exchange interaction in Ce4Pt12Sn25 is responsible for its low ordering temperature and a negligible Kondo-derived contribution to physical properties above T(N). The anomalous enhancement of specific heat above T(N) is suggested to be related, in part, to weak geometric frustration of f-moments in this compound.

Single crystals of the new Zintl phases AIn2P2 [A = Ca (calcium indium phosphide), Sr (strontium indium phosphide) and Ba (barium indium phosphide)] have been synthesized from a reactive indium flux. CaIn2P2 and SrIn2P2 are isostructural with EuIn2P2 and crystallize in the space group P63/mmc. The alkaline earth cations A are located at a site with 3m symmetry; In and P are located at sites with 3m symmetry. The structure type consists of layers of A2+ cations separated by [In2P2]2- anions that contain [In2P6] eclipsed ethane-like units that are further connected by shared P atoms. This yields a double layer of six-membered rings in which the In-In bonds are parallel to the c axis and to one another. BaIn2P2 crystallizes in a new structure type in the space group P2(1)/m with Z = 4, with all atoms residing on sites of mirror symmetry. The structure contains layers of Ba2+ cations separated by [In2P2]2- layers of staggered [In2P6] units that form a mixture of four-, five- and six-membered rings. As a consequence of this more complicated layered structure, both the steric and electronic requirements of the large Ba2+ cation are met.

Single crystals of EuGa2Pn2 (Pn=P, As) were grown from a molten Ga flux and characterized by single-crystal X-ray diffraction at 100(1) K. They are isostructural and crystallize in a new structure type (monoclinic, P2/m, a=9.2822(9) A, =3.8967(4) A, c=12.0777(11) A, Β=95.5220(10), R1= 0.0148, wR2=0.0325 (EuGa2P2) and a=9.4953(7) A, b=4.0294(3) A, c=12.4237(9) A, Β =95.3040(10), R1=0.0155, wR2=0.0315 (EuGa2As2)). The structures consist of alternating layers of two-dimensional Ga2Pn2 anions and Eu cations. The anion layers are composed of Ga2Pn6 staggered, ethane-like moieties having a rare Ga-Ga bonding motif; these moieties are connected in a complex fashion bymeans of shared Pn atoms. Both structures showsmall residual electron densities that can be modeled by adding a Eu atom and removing two bonded Ga atoms, resulting in structures (< 2%) wheremost of the atoms are the same, but there is a difference in bonding that leads to one-dimensional ribbons of parallel Ga2Pn6 staggered, ethane-like moieties. The compounds can be understood within the Zintl formalism, but show metallic resistivity. Magnetization measurements performed on single crystals show low-temperature magnetic anisotropy as well as multiple magnetic ordering events that occur at and below 24 and 20 K for the phosphorus and arsenic analogs, respectively. The magnetic coupling between Eu ions is attributed to indirect exchange via an RKKY interaction, which is consistent with the metallic behavior. The compounds display large negative magnetoresistance of up to-80 and-30%(MR=[(F(H)-F(0))/F(H)] 100%) for Pn=P,As, respectively,which is maximal at the magnetic ordering temperatures in the highest measured field (5T).

The temperature dependence of the specific heat and of the resistivity under pressure has been measured for single crystals of the semiconductor Ce3 Au3 Sb4. The transport data follow an exponential activation and variable range hopping at low T, consistent with weak disorder and localization, while C / T has a - ln T dependence with large entropy. Thus the properties of Ce3 Au3 Sb4 are very different from those of ordinary Kondo insulators. © 2007.

The magnetic, thermal, and transport properties of single crystals of the narrow gap semiconductor Ce3 Au3 Sb4 have been studied. Transport data are consistent with an exponential activation and variable range hopping at low temperatures, which is characteristic of weak disorder and localization. The specific heat and the magnetic susceptibility data suggest the existence of a large density of states of localized states in the gap. The physics is then different from standard Kondo insulators. From its unique physical properties, we propose a three band model (valence, conduction, and f bands) with weak disorder that explains most of the experimental findings. © 2007 The American Physical Society.

Ln3Co4Sn13 (Ln=La, Ce) have been synthesized by flux growth and characterized by single crystal X-ray diffraction. These compounds adopt the Yb3Rh4Sn13-type structure and crystallize in the cubic space group Pm over(3, -) n (No. 223) with Z = 2. Lattice parameters at 298 K are a = 9.6430 ( 6 ) Å, V = 896.68 ( 10 ) Å3, and a = 9.6022 ( 5 ) Å, V = 885.34 ( 8 ) Å3 for the La and Ce analogues, respectively. The crystal structure consists of an Sn-centered icosahedron at the origin of the unit cell, which shares faces with eight Co trigonal prisms and 12 Ln-centered cuboctahedra. Magnetization data at 0.1 T show paramagnetic behavior down to 1.8 K for Ce3Co4Sn13, with μeff = 2.56 μB per Ce3+, while conventional type II superconductivity appears below 2.85 K in the La compound. Electrical resistivity and specific heat data for the La compound show a corresponding sharp superconducting transition at Tc∼2.85 K. The entropy and resistivity data for Ce3Co4Sn13 show the existence of the Kondo effect with a complicated semiconducting-like behavior in the resistivity data. In addition, a large enhanced specific heat coefficient at low T with a low magnetic transition temperature suggests a heavy-fermionic character for the Ce compound. Herein, the structure and physical properties of Ln3Co4Sn13 (Ln=La, Ce) are discussed. © 2006 Elsevier Inc. All rights reserved.

A new rare earth metal Zintl phase, Eu(3)In(2)P(4), was synthesized by utilizing a metal flux method. The compound crystallizes in the orthorhombic space group Pnnm with the cell parameters a = 16.097(3) A, b = 6.6992(13) A, c = 4.2712(9) A, and Z = 2 (T = 90(2) K, R1 = 0.0159, wR2 = 0.0418 for all data). It is isostructural to Sr(3)In(2)P(4). The structure consists of tetrahedral dimers, [In(2)P(2)P(4/2)](6-), that form a one-dimensional chain along the c axis. Three europium atoms interact via a Eu-Eu distance of 3.7401(6) A to form a straight line triplet. Single-crystal magnetic measurements show anisotropy at 30 K and a magnetic transition at 14.5 K. High-temperature data give a positive Weiss constant, which suggests ferromagnetism, while the shape of susceptibility curves (chi vs T) suggests antiferromagnetism. Heat capacity shows a magnetic transition at 14.5 K that is suppressed with field. This compound is a semiconductor according to the temperature-dependent resistivity measurements with a room-temperature resistivity of 0.005(1) Omega m and E(g) = 0.452(4) eV. It shows negative magnetoresistance below the magnetic ordering temperature. The maximum magnetoresistance (Deltarho/rho(H)) is 30% at 2 K with H = 5 T.

Eu3InP3 has been prepared as large single crystals with an indium flux reaction. The structure of the new compound is isotypic to Sr3InP3 and crystallizes in the orthorhombic space group Pnma with unit cell dimensions of a = 12.6517(15) A, b = 4.2683(5) A, and c = 13.5643(14) A (Z = 4, T = 140 K, R1 = 0.0404, wR2 = 0.0971 for all data). The structure consists of one-dimensional chains of corner-shared distorted [InP2P2/2]6- tetrahedra separated by rows of Eu2+ ions. Two of the three crystallographically distinct europium sites have a short Eu(1)-Eu(2) distance of 3.5954(7) A, which yields Eu-Eu dimers. The Eu-P bond distances range from 2.974(2) to 3.166(2) A. The temperature dependence of the conductivity indicates that Eu3InP3 is a small band gap semiconductor. Both magnetization and Eu-151 Mossbauer spectral measurements indicate that the europium in Eu3InP3 is divalent and that at least two magnetic transitions occur. Magnetization studies reveal magnetic transitions at 14, 10.4, and approximately 5 K. These transitions are also observed in heat capacity studies of Eu3InP3. The Mossbauer spectra indicate that the two europium sites are ordered at 12 K and that all three europium sites are ordered at 8 K.

Research has been conducted on the coordinate complexes. The reaction of M{N(SiMe (sub)3) (sub)2} (sub)2 (M= Mn, Re, Co) with different beta-diketimines has produced three-coordinate complexes characterized via magnetic measurements, X-ray crystallography and NMR and IR spectroscopy and the details are included.

Unconventional superconductors have Cooper pairs with lower symmetries than in conventional superconductors. In most unconventional superconductors, the additional symmetry breaking occurs in relation to typical ingredients such as strongly correlated Fermi liquid phases, magnetic fluctuations, or strong spin-orbit coupling in noncentrosymmetric structures. In this article, we show that the time-reversal symmetry breaking in the superconductor LaNiGa2 is enabled by its previously unknown topological electronic band structure, with Dirac lines and a Dirac loop at the Fermi level. Two symmetry related Dirac points even remain degenerate under spin-orbit coupling. These unique topological features enable an unconventional superconducting gap in which time-reversal symmetry can be broken in the absence of other typical ingredients. Our findings provide a route to identify a new type of unconventional superconductors based on nonsymmorphic symmetries and will enable future discoveries of topological crystalline superconductors. Topological superconducting systems are expected to exhibit a range of exotic physics which are particularly useful for application in quantum computing technologies. Here, the authors report the synthesis of LaNiGa2 which exhibits both topological and superconducting features originating from its nonsymmorphic crystal structure. [ABSTRACT FROM AUTHOR]

Eu3InP3 is prepared as large single crystals with an indium flux reaction. The temperature dependence of the conductivity indicates that Eu3InP3 is a small band gap semiconductor.

Research has been conducted on transitio-metal-containing Zintl compound Eu (sub)10 Mn (sub)6 Sb (sub)13. The authors describe the preparation of this compound via high-temperature tin-flux synthesis, and report that its structure has been investigated via the use of single-crystal X-ray diffraction.