Structural and Thermodynamic Properties of the Cm(III) Ion Solvated by Water and Methanol.
The geometric and electronic structures of the 9-coordinate Cm(3+) ion solvated with both water and methanol are systematically investigated in the gas phase at each possible solvent-shell composition and configuration using density functional theory and second-order Møller-Plesset perturbation theory. Ab initio molecular dynamics simulations are employed to assess the effects of second and third solvent shells on the gas-phase structure. The ion-solvent dissociation energy for methanol is greater than that of water, potentially because of increased charge donation to the ion made possible by the electron-rich methyl group. Further, the ion-solvent dissociation energy and the ion-solvent distance are shown to be dependent on the solvent-shell composition. This has implications for solvent exchange, which is generally the rate-limiting step in complexation reactions utilized in the separation of curium from complex metal mixtures that derive from the advanced nuclear fuel cycle.
Department of Chemistry, Washington State University , Pullman, Washington 99164, United States.|Theoretical Division, Los Alamos National Laboratory , Los Alamos, New Mexico 87544, United States.
Morgan P
MP
Kelley
Theoretical Division, Los Alamos National Laboratory , Los Alamos, New Mexico 87544, United States.
Ping
P
Yang
Department of Chemistry, Washington State University , Pullman, Washington 99164, United States.
Sue B
SB
Clark
Department of Chemistry, Washington State University , Pullman, Washington 99164, United States.
Aurora E
AE
Clark