Zintl phases form hydrides either by incorporating hydride anions (interstitial hydrides) or by covalent bonding of H to the polyanion (polyanionic hydrides), which yields a variety of different compositions and bonding situations. Hydrides (deuterides) of SrGe, BaSi, and BaSn were prepared by hydrogenation (deuteration) of the CrB-type Zintl phases AeTt and characterized by laboratory X-ray, synchrotron, and neutron diffraction, NMR spectroscopy, and quantum-chemical calculations. SrGeD and BaSnD show condensed boatlike six-membered rings of Tt atoms, formed by joining three of the zigzag chains contained in the Zintl phase. These new polyanionic motifs are terminated by covalently bound H atoms with d(Ge-D) = 1.521(9) Å and d(Sn-D) = 1.858(8) Å. Additional hydride anions are located in Ae tetrahedra; thus, the features of both interstitial hydrides and polyanionic hydrides are represented. BaSiD retains the zigzag Si chain as in the parent Zintl phase, but in the hydride (deuteride), it is terminated by H (D) atoms, thus forming a linear (SiD) chain with d(Si-D) = 1.641(5) Å.
Topological insulators constitute a new class of materials with an energy gap in the bulk and peculiar metallic states on the surface. We report on new features resulting from the bulk electronic structure, based on a comprehensive nuclear magnetic resonance (NMR) study of 77 Se on Bi 2 Se 3 and Cu 0.15 Bi 2 Se 3 single crystals. First, we find two resonance lines and show that they originate from the two inequivalent Se lattice sites. Second, we observe unusual field-independent linewidths and attribute them to an unexpectedly strong internuclear coupling mediated by bulk electrons. In order to support this interpretation, we present a model calculation of the indirect internuclear coupling and show that the Bloembergen-Rowland coupling is much stronger than the Ruderman-Kittel-Kasuya-Yosida coupling. Our results call for a revision of earlier NMR studies and add information concerning the bulk electronic properties.
Planar oxygen nuclear magnetic resonance (NMR) relaxation and shift data from all cuprate superconductors available in the literature are analyzed. They reveal a temperature-independent pseudogap at the Fermi surface, which increases with decreasing doping in family-specific ways, i.e., for some materials, the pseudogap is substantial at optimal doping while for others it is nearly closed at optimal doping. The states above the pseudogap, or in its absence are similar for all cuprates and doping levels, and Fermi liquid-like. If the pseudogap is assumed exponential it can be as large as about 1500 K for the most underdoped systems, relating it to the exchange coupling. The pseudogap can vary substantially throughout a material, being the cause of cuprate inhomogeneity in terms of charge and spin, so consequences for the NMR analyses are discussed. This pseudogap appears to be in agreement with the specific heat data measured for the YBaCuO family of materials, long ago. Nuclear relaxation and shift show deviations from this scenario near Tc, possibly due to other in-gap states.
Cuprate superconductors still hold many open questions, and recently, the role of symmetry breaking electronic charge ordering resurfaced in underdoped cuprates as phenomenon that competes with superconductivity. Here, unambiguous NMR proof is presented for the existence of local charge ordering in nearly optimally doped YBa2Cu3O6.9, even up to room temperature. Increasing pressure and decreasing temperature leads to the highest degree of order in the sense that the two oxygen atoms of the unit cell of the CuO2 plane develop a charge difference of about 0.02 holes, and order throughout the whole crystal. At ambient conditions a slightly smaller charge difference and a decreased order is found. Evidence from literature data suggests that this charge ordering is ubiquitous to the CuO2 plane of all cuprates. Thus, the role of charge ordering in the cuprates must be reassessed.
Very recently, nuclear magnetic resonance (NMR) of 209 Bi has been shown to provide quantitative access to the bulk band inversion in the topological insulator Bi 2 Se 3 and detected a highly unusual field induced charge rotation that was found also in the closely related topological insulator Bi 2 Te 3 . These observations revealed special properties of the electronic fluid but also reshaped the comprehension of NMR in strongly spin−orbit coupled systems. Here, 209 Bi NMR of Bi 2 Te 3 of two single crystals with different carrier concentrations is presented, which expands the experimental basis of the unusual charge rotation and the related nuclear spin−lattice relaxation mechanism.
The Zintl phase deuterides CaSiD4/3, SrSiD5/3, BaSiD2, SrGeD4/3, BaGeD5/3 and BaSnD4/3 were investigated by nuclear magnetic resonance (NMR) spectroscopy and density functional theory (DFT) calculations to reliably determine element–deuterium bond lengths.
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