Rh. Mitchell et al., Crystal chemistry of perovskite-type compounds in the tausonite-loparite series, (Sr1-2xNaxLax)TiO3, PHYS CHEM M, 27(8), 2000, pp. 583-589
Perovskite-type compounds in the series tausonite-loparite, (Sr1-2xNaxLax)T
iO3, were synthesized by solid-state reaction (final heating at 1200-1300 d
egrees C), and studied using "conventional" and synchrotron X-ray powder di
ffractometry. The structures of intermediate compositions were determined u
sing the Rietveld profile refinement method. In the compositional range 0 l
ess than or equal to x less than or equal to 0.1, the series comprises pero
vskites characterized by an undistorted cubic structure (space group Pm (3)
over bar m, a approximate to 3.905 3.902 Angstrom, Z = 1). Intermediate co
mpounds in the range 0.15 less than or equal to x less than or equal to 0.3
5 crystallize with tetragonal symmetry (I4/mcm, a approximate to root 2a(p)
, c approximate to root 2a(p), Z = 4) derived from the cubic aristotype by
antiphase rotation of the TiO6 octahedra about a fourfold axis. The angle o
f rotation estimated from the positional parameters of oxygen atoms ranges
from 2.5(7)degrees to 5.5(4)degrees. The cubic-to-tetragonal transition ari
ses from substitution of Sr2+ by the comparatively smaller Na1+ and La3+ ca
tions. A further transition from the tetragonal to rhombohedral symmetry (R
(3) over bar c, a approximate to root 2a(p), c approximate to 2 root 3a(p)
, Z = 6) occurs between x = 0.35 and 0.40, and apparently does not involve
formation of perovskite with an intermediate two-tilt structure (Imma). The
rhombohedral structure is characterized by a multicomponent octahedral til
t about a threefold axis ranging in magnitude from 6.5(2)degrees to 7.7(2)d
egrees. In the series (Sr1-2xNaxLax)TiO3, the unit-cell dimensions decrease
, and the degree of structural distortion increases with x.