We have established a plot of the anion height dependence of superconducting transition temperature T c for the typical Fe-based superconductors. The plot showed a symmetric curve with a peak around 1.38 Å. Both data at ambient pressure and under high pressure obeyed the unique curve. This plot will be one of the key strategies for both understanding the mechanism of Fe-based superconductivity and search for the new Fe-based superconductors with higher T c .2
Ferromagnetism and superconductivity are thought to compete in conventional superconductors, although in principle it is possible for any metal to become a superconductor in its non-magnetic state at a sufficiently low temperature. At pressures above 10 GPa, iron is known to transform to a non-magnetic structure and the possibility of superconductivity in this state has been predicted. Here we report that iron does indeed become superconducting at temperatures below 2 K at pressures between 15 and 30 GPa. The transition to the superconducting state is confirmed by both a drop in resistivity and observation of the Meissner effect.
Electron localization in the bulk condensed phases of acetonitrile differs drastically from the corresponding processes that take place in water and aliphatic alcohols. In particular, electron capture following the ionization of liquid and solid acetonitrile yields well-defined radical anions in place of the largely structureless solvated and trapped electrons characteristic of irradiated solutions and rigid glasses. This is remarkable given the many similarities that exist not only between the intrinsic properties of these individual solvent molecules, such as polarity, but also in their cooperative capacity to function as solvents. Here, with the aid of detailed experimental and computational studies, we examine on a fundamental level what gives rise to such a sharp contrast in the behavior of these alkyl cyanides as compared to water and alcohols. EPR and optical spectra, and ab initio calculations on the radical anions are used together with diffraction data for the crystal structures to demonstrate that electron attachment to nitrile molecules in the crystalline state results in a significant bending of the linear CCN moiety. Moreover, in the formation of the dimer anions, which only takes place in certain crystalline phases, it is determined that the intermolecular bonding occurs between the cyanide carbons in an antiparallel arrangement. A staggered structure for the dimer anion in R-acetonitrile is then suggested, in which there is a nearly coplanar arrangement with the two bent CCN fragments. The resulting structure accounts for the observed EPR parameters, the position of the UV-vis absorption band, and the trends observed in the vibronic progressions for the four H/D isotopomers. The dimer radical anion in R-acetonitrile retains the same orientation and symmetry as that of the preexisting neutral {CH 3 CN} 2 pairs in this crystal despite the resulting changes in molecular geometry and in the translational coordinates for the cyanide carbons as the two acetonitrile molecules come together. We suggest that dimer anions of nitriles can form only in the phases where such "antiparallel" pairs occur, including liquid systems; otherwise, the electron remains attached to a single molecule, as in β-acetonitrile. Because electron capture by water or alcohol molecules in the condensed phase appears to require larger molecular clusters, the contrast between the behavior of these solvents and acetonitrile is attributable to the relative ease with which acetonitrile molecules in the crystal or solvent can undergo valence-electron attachment via their accessible low-lying π* orbitals.
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