Synchrotron X-ray analysis of RbTiOAsO4

Abstract

Structure factors for rubidium oxotitanium arsenate, RbTiOAsO4, were measured at 293 K with focused synchrotron X-radiation [λ = 0.7500 (9) Å] using a fast avalanche photodiode counter. The accurate synchrotron single-crystal data are of sufficient quality and resolution to detect the splitting positions of the Rb cations at room temperature. Strong accumulation of the Δρ difference charge density near the Rb atoms at a distance of ∼0.5 Å in the −c direction can be attributed to the partial occupancy of additional sites related by pseudosymmetry. This type of static and/or dynamic disorder is temperature-dependent and seems to be universal for the KTiOPO4 family of compounds. The best modelling of the experimental data was obtained with the Rb atom in split positions described within the harmonic approximation and the multipole functions for the other atoms. The Δρ density features in the Ti—O and As—O covalent bonds can be related to the linear and non-linear susceptibility using bond-polarization theory. The charge-density maps reflect the anisotropy of non-linear susceptibility, which is larger for directions where locally antisymmetric components of Δρ are strong.