The blue bronze Tl 0.30MoO 3 structure and physical properties

Abstract

Crystals of the so-called blue bronze Tl 0.30MoO 3 were prepared by tempering molten mixtures. The structure was refined in the space group C2/m from 2171 reflections corrected for absorption. The R and R w factors obtained from the last refinement cycle are 0.030 and 0.036 respectively for 114 refined parameters. The Zachariasen method enabled the 4d distribution over the three independent sites Mo1, Mo2 and Mo3 to be determined and gave 16.6 %, 39.7 % and 43.7 % respectively. For each octahedron a close correlation appears between the number of shared edges, the formal molybdenum charge and its eccentricity within the polyhedron. It is found that the molybdenum Mo1 has the highest formal charge ; this site does not seem to participate in the electrical conductivity which takes place mainly in the slabs thanks to the molybdenum sites Mo2 and Mo3 which represent 83.4 % of the electron density. Tl 0.30MoO 3 shows a metal-to-semiconductor transition at 185 K, probably of Peierls type. We propose that the non-linear effects and metastability phenomena observed below 180 K, in the non-ohmic regime are very likely due to the depinning of a charge density wave, as it has been found in the blue bronze K 0.30MoO 3