Structural instability and electronic localization in the 2:1 salts: The case of the Fabre and the (DMtTTF)2CIO4salts

The charge ordering observed in the (TMTTF) 2 X family has been studied by X-ray absorption spectroscopy. XANES measurements at the Sulfur K-edge show no evidence of charge disproportionation larger than 0.5 e, and EXAFS at the Phosphorus K-edge indicate no displacements of the PF 6 anion larger than 0.05 A. The difficulty to observe a structural signature of this charge ordering is due to the triclinic symmetry of these salts. By contrast, in the monoclinic charge transfer salt (DMtTTF) 2 ClO 4 , a screw axis symmetry constrains the molecular stacks to be uniform. In this real 1/4-filled system, charge localization is observed at about 150 K. We show that around this temperature an incommensurate modulation of reduced wave vector (0.58,0,-0.275) is stabilized. The transition is strongly hysteretic, but no long range order is established. We suggest that this modulation, which has the 4kF periodicity in the chain direction, stabilizes a local antiferroelectric state similar to the one previously observed in (TMTTF) 2 SCN.