The spectroscopic properties of the Mn⁴⁺ (3d³) ion in the orthorhombic perovskites ABO₃ (A = Ca, Sr; BZr⁴⁺) is the subject of this investigation. The optical properties of the Mn⁴⁺ ion in CaZrO₃ is sensitive to oxygen stoichiometry. Comparison with the reported optical properties of oxygen-stoichiometric CaZrO₃:Mn⁴⁺ obtained by synthesizing in oxygen atmosphere indicates that the air sintered sample represents Mn⁴⁺ luminescence in an oxygen deficient perovskite lattice. The luminescence of SrZrO₃:Mn⁴⁺ suggests that this perovskite is less prone to the formation of oxygen vacancies. The difference between the energies of the zero-phonon line (²E→⁴A₂ transition; R-line) in CaZrO₃ and SrZrO₃ is related to the deviation of the octahedral O–Mn–O bond angle from the ideal 90° value. Comparison with isostructural perovskites ASnO₃ (A = Ca, Sr) shows that the energy of the ²E level depends on the covalent character of B–O bonding. The stronger covalence of Zr⁴⁺ 4d⁰- O²⁻ 2p bonding compared to that of Sn⁴⁺ 4d¹⁰ - O²⁻ 2p bonding is responsible for the higher energy position of the Mn^{4+ 2}E level in the zirconate perovskite. Mulliken population analysis and bond order calculations are made to understand the nature of chemical bonding in the perovskites ABO₃ (A = Ca, Sr; B= Zr⁴⁺, Sn⁴⁺).

正交晶系钙钛矿A B O ₃（A = Ca，Sr; B Zr ⁴⁺）中Mn ⁴⁺（3 d ³）离子的光谱性质是本研究的主题。CaZrO _3中Mn ⁴⁺离子的光学性质对氧化学计量敏感。与通过在氧气气氛中合成而获得的氧气化学计量的CaZrO ₃：Mn ⁴⁺的报道的光学性质进行比较表明，空气烧结的样品在缺氧的钙钛矿晶格中表现出Mn ⁴⁺发光。SrZrO ₃：Mn ⁴⁺的发光表明钙钛矿不太容易形成氧空位。CaZrO ₃和SrZrO _3中零声子线（² E→ ⁴ A ₂跃迁； R线）的能量之差与八面体O-Mn-O键角与理想90°的偏差有关价值。与等结构钙钛矿ASnO ₃（A = Ca，Sr）的比较表明，² E能级的能量取决于B – O键的共价特征。与Sn ⁴⁺ 4d ¹⁰相比，Zr ⁴⁺ 4d ⁰ -O ²⁻ 2p键的共价性更强-O ²⁻ 2p键是锆酸钙钛矿中Mn ^{4+ 2} E能级较高的能量位置。进行了Mulliken种群分析和键序计算，以了解钙钛矿A B O ₃（A = Ca，Sr；B = Zr ⁴⁺，Sn ⁴⁺）中化学键的性质。