Na atomic order, Co charge disproportionation and magnetism in Nax_{x}CoO2_{2} for large Na contents

We have synthesized and characterized four different stable phases of Na ordered Na$_{x}$CoO$_{2}$, for $0.65<x<0.8$. Above 100 K they display similar Curie-Weiss susceptibilities as well as ferromagnetic $q=0$ spin fluctuations in the CoO$_{2}$ planes revealed by $^{23}$Na NMR data. In all phases from $^{59}$Co NMR data we display evidences that the Co disproportionate already above 300 K into non magnetic Co$^{3+}$ and magnetic $\approx$Co$^{3.5+}$ sites on which holes delocalize. This allows us to understand that metallic magnetism is favored for these large Na contents. Below 100 K the phases differentiate, and a magnetic order sets in only for $x\gtrsim 0.75$ at $T_{N}=$22 K. We suggest that the charge order also governs the low $T$ energy scales and transverse couplings

59Co NMR study of the Co states in superconducting and anhydrous cobaltates

$^{59}$Co NMR spectra in oriented powders of Na$_{0.35}$CoO$_{2}$ and in its hydrated superconducting phase (HSC) Na$_{0.35}$CoO$_{2}$,1.3H$_{2}$O reveal a single electronic Co state with identical $T$ independent NMR shift tensor. These phases differ markedly from Na$_{0.7}$CoO$_{2}$, in which we resolve 3 types of Co sites. The large T variation of their spin susceptibilities $\chi ^{s}$ and the anisotropy of the orbital susceptibility $\chi ^{orb}$ allow us to conclude that charge disproportionation occurs, in a non magnetic Co$^{3+}$ and two magnetic sites with about 0.3 and 0.7 holes in the $t_{2g}$ multiplet. The data are consistent with those for the single Co site in the anhydrous and HSC phase assuming the expected Co$^{3.65+}$ charge.Comment: 5 pages, 3 figures, accepted for publication in Phys. Rev. Let

Antiferromagnetic properties of a water-vapor-inserted YBa₂Cu₃O_6.5 compound studied by NMR, NQR, and &mu;SR

We present a detailed NQR, NMR and $\mu$SR study of a magnetic phase obtained during a topotactic chemical reaction of YBa$_{2}$Cu$_{3}$O$_{6.5}$ high- temperature superconductor with low-pressure water vapor. Our studies give straightforward evidence that the ''empty'' Cu(1) chains play the role of an easy water insertion channel. It is shown that the NQR spectrum of the starting material transforms progressively under insertion of water, and completely disappears when one H$_{2}$O molecule is inserted per unit cell. Similarly, a Cu ZFNMR signal characteristic of this water inserted material appears and grows with increasing water content, which indicates that the products of the reaction are non-superconducting antiferromagnetic phases in which the bilayers are ordered. These antiferromagnetic phases are felt by proton NMR which reveals two sites with static internal fields of 150 and about 15 Gauss respectively. Two muon sites are also evidenced with similar local fields which vanish at $T\approx 400$ K. This indicates that the magnetic phases have similar N\'{e}el temperatures as the other bilayer undoped compounds. An analysis of the internal fields on different sites of the structure suggests that they can be all assigned to a single magnetic phase at large water content in which the Cu(1) electron spins order with those of the Cu(2). It appears that even samples packed in Stycast epoxy resin heated moderately at a temperature (200$^{0}$C) undergo a reaction with epoxy decomposition products which yield the formation of the same final compound. It is then quite clear that such effects should be considered quite seriously and avoided in experiments attempting to resolve tiny effects in such materials, as those performed in some recent neutron scattering experiments.Comment: 12 pages of revised text including 12 Figure