Theoretical analysis of electronic and structural properties of anhydrous calcium oxalate

The results of theoretical analysis of the electronic and crystal structural properties and bonding in relation to thermal decomposition process in anhydrous calcium oxalate are presented. The methods used in this analysis—topological analysis of electron density (Bader’s Quantum Theory of Atoms in Molecules approach) obtained from DFT calculations performed by Wien2k package (Full Potential Linearized Augmented Plane Wave Method); bond order model (Cioslowski&Mixon), applied to topological properties of the electron density; as well as Brown’s Bond Valence Model (bonds valences and strength’, and bond and crystal strains, calculated from crystal structure and bonds lengths data) are described. The analysis of the obtained results shows that these methods allow us to explain the way of thermal decomposition process of anhydrous calcium oxalate to calcium carbonate as a decomposition product, and to describe the structural transition taking place during such process (from monoclinic anhydrous CaC₂O₄ to rhombohedral calcite structure). In the light of the results of our similar calculations performed previously for other anhydrous oxalates (zinc, cadmium silver, cobalt, and mercury) the proposed theoretical approach can be considered as promising and reliable tool, which allow analyzing the properties of the structure and bonding and hence predicting the most probable way of thermal decomposition process for given crystal structure.