Theoretical Study on the Thermal Decomposition Mechanism of Fe(EDTA)− and Fe(EDTMP)−

The decomposition mechanisms of Fe(EDTA)^- and Fe(EDTMP)^- complexes, widely used in various industrial applications, were investigated through a theoretical approach. Despite their structural similarities, the phosphonic acid and carboxylic acid groups in these complexes lead to vastly different decomposition behaviors. Fe(EDTA)^-, stabilized by delocalized π bonds in carboxylic acid groups, exhibited higher stability than that of Fe(EDTMP)^-, which has only σ bonds in phosphonic acid groups. Interaction Region Indicator (IRI) analysis revealed that the steric hindrance of Fe(EDTMP)^- was stronger than that of Fe(EDTA)^-. Ab initio molecular dynamics simulations revealed that Fe(EDTMP)^- undergoes rapid decomposition due to the ease of breaking P-C bonds and the repulsion between phosphonic acid groups. In contrast, Fe(EDTA)^- decomposes more slowly. These findings suggest the incorporation of phosphonic acid groups for easier degradation pathways when designing organic acid molecules. Understanding these mechanisms provides a basis for developing strategies for wastewater treatment in industrial settings.