Theoretical insights into the coordination structures, stabilities and electronic spectra of Cm³⁺ species at the...

The information of structure and stability of actinide species is key to understand the sorption mechanism of actinides at mineral-water interface. Such information is approximately derived from experimental spectroscopic measurements and needs to be accurately obtained by a direct atomic-scale modelling. Herein, systematic first-principles calculations and ab initio molecular dynamics (AIMD) simulations are carried out to study the coordination structures and absorption energies of Cm(III) surface complexes at gibbsite-water interface. Eleven representative complexing sites are investigated. The most stable Cm³⁺ sorption species are predicted to be a tridentate surface complex in weakly acidic/neutral solution condition and a bidentate one in the alkaline solution condition. Moreover, luminescence spectra of the Cm³⁺ aqua ion and the two surface complexes are predicted based on the high-accuracy ab initio wave function theory (WFT). The results give a gradually decreasing emission energy in good agreement with experimental observation of a red shift of peak maximum with pH increasing from 5 to 11. This work is a comprehensive computational study involving AIMD and ab initio WFT methods to gain the coordination structures, stabilities, and electronic spectra of actinide sorption species at the mineral-water interface, thus providing important theoretical support for geological disposal of actinide waste.