Atomic ordering of the fluorine dopant in theHgBa2CuO4+δhigh-T

Lattice sites and collective ordering of fluorine atoms in oxygen- reduced samples of HgBa/sub 2/CuO/sub 4/ were investigated with the perturbed angular correlation technique by measuring the electric field gradients induced at /sup 199m/Hg nuclei. The experimental data were interpreted with the help of ab initio calculations of charge distributions for different fluorine configurations in Hg/sub m/Ba /sub 2m/Cu/sub m/O/sub 4m/F/sub n/, supercells. Internal parameters were allowed to relax, to cancel residual atomic forces due to the dopant. The experimental results show clearly that fluorine occupies only the center of the mercury mesh. For a fluorine content delta F>~0.35 the best agreement with theoretical data is obtained under the assumption that fluorine shows a tendency toward ordering along interstitial rows parallel to a, b. In conformity with experimental data from diffraction techniques the calculations show elongations of the O(2)-Hg-O(2) dumbbell and barium shifts towards the fluorine atoms as effects of the dopant. No strong ordering of the transferred charge at the copper planes is present in the computed charge density, even when the fluorine atoms order at high concentrations