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Aminopolycarboxylic acids such as 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) are widely used in the nuclear field as a chelating agent. Consequently, they may degrade under radiolysis during applications or after disposal, and their degradation mechanism has been investigated. In this work, the decarboxylation reaction of DOTA in water solution was modeled using DFT calculations, as observed experimentally. The reaction involves an intermediate state and two energy barriers. Deprotonated DOTA presents a more complex decarboxylation reaction path, with two intermediate states and three transition states. Deprotonation was found to cut the energy barrier to about half, facilitating the degradation. These results reinforce the importance of radicals produced by the radiolysis of water in the degradation of DOTA, as seen for other materials. Host: Enrique Batista (T-CNLS) | ||||||||