Impurity structure in a molecular ionic crystal: Atomic-scale x-ray study of CaCO3 : Mn2+ - art. no. 144104

The lattice sites and spatial disorder of isolated Mn2+ ions in calcite wer e examined with x-ray standing waves, and the structure of the surrounding ions was examined with extended x-ray absorption fine-structure spectroscop y, The Mn2+ ion is found to be on-center substitutional at the Ca2+ site, w ith spatial disorder comparable to that of Ca2+. The first-neighbor Mn-O di stance is found to be the same as that in the isostructural MnCO3. The radi al distance of the closest Mn-Ca shell is reduced by similar to2% from the undistorted Ca-Ca distance. Based on these measurements, an atomic-scale st ructural model of the Mn2+ site suggests that the intramolecular distortion in the first-neighbor CO32- anions plays a key role in establishing the co nserved first-neighbor Mn-O distance while maintaining ordering with respec t to the lattice. The CaCO3:Mn2+ structure is shown to be characteristicall y distinct from those of analogous impurities in monatomic ionic crystals.