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Early actinide elements (from U to Am) have the ability to form linear trans-dioxo complexes with formal valence of the actinide being equal to (V) or (VI). For instance, the ubiquity of the uranyl cation in uranium aqueous chemistry is the basis for its very important industrial and environmental concerns. As a result, the physical chemistry of the actinyl moieties has been the subject of constantly growing investigations. Among all the spectroscopic probes, X-ray absorption spectroscopy is a particularly useful element and energy-selective technique.