The significance of the Jahn-Teller effect for the phase transitions of K2NbCl6 and Rb2NbCl6

Abstract

X-ray powder measurements were used to investigate the phase transitions and crystal structures of K2NbCl6 and Rb2NbCl6. In both cases, the metrical changes of the unit cell are accompanied by a compressive distortion of the NbCl6 2− groups from O h to D 4h symmetry. This static manifestation of the Jahn-Teller effect is ascribed to electro static interactions with the cations. Thus, Rb2NbCl6 trans forms from Fm-3m (Z = 4) to I4/mmm (Z = 2) due to a cation-supported compression in the c direction, whereas K2NbCl6 expands along c when converting from Fm-3m to P4/mnc (Z = 2). On further cooling a second transition leads to Cccm (Z = 4) where b as the shortest axis is approximately parallel to the direction of the octahedral contraction. The oxidation state of Nb4+ (d 1) is checked via bond-length bond-strength correlations and magnetic measurements.