Crystal structure, atomic net charges and electric moments in pyroelectric LiNaSO4 at 296 K.

Abstract

The crystal structure and electric charge distribution in LiNaSO4 have been studied at 296 K by X-ray diffraction using a spherical crystal. LiNaSO4 is pyroelectric, nonferroelectric and an optically uniaxial insulator which crystallizes in the space group P31c. Least-squares refinement (MOLLY) was based on 13,026 reflections. The asymmetric unit contains Li(+), Na(+) and three SO4(2-) ions, where one O and S lie on a threefold axis about which three O atoms are related with a threefold symmetry in each sulfate ion. Two of the O-S-O groups suffer from disorder. The net charges of the atoms in three independent sulfate ions were determined under ionic charge constraints. The S atoms have positive net electric charges and O atoms are negative. The components of the significant electric multipole moments in the principal axis directions are determined from the distribution of net atomic charges in each sulfate ion. Electric moments in the unit cell generate macroscopic electric moments in the crystal which interact with light. This interaction results in two axial vectors of second rank associated with an optical indicatrix. The ratio of the calculated axial vector components in the principal axis directions originating from the asymmetric unit is 1.0061 (1), which compares well with the ratio of 1.006 for the corresponding optical refractive indices of LiNaSO4 for λ(Na) = 589.29 nm.