Abstract
The aim of this paper is to provide a comparative study of the spectroscopic properties of Mn4+ (3d3) ion in the orthorhombic perovskites, ASnO3 (A=Ca, Sr). The most significant parameter controlling the energy of the zero-phonon line (2E→4A2 transition) is the deviation of the octahedral O-Mn-O bond angle from the ideal 900 value. It is significant that despite the longer Sn4+-O2- bond distance, the crystal field strength (10 Dq) in CaSnO3 is higher than that of SrSnO3. We discuss this result in relation to the perovskite crystal chemistry. Mulliken population analysis and bond order calculation are made to clarify the nature of chemical bonding in the stannate perovskites.
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