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Title: Structural and thermodynamic properties of the CmIII ion solvated by water and methanol

The geometric and electronic structures of the 9-coordinate Cm3+ 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. Furthermore, 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.
Authors:
 [1] ;  [2] ;  [3] ;  [3]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Washington State Univ., Pullman, WA (United States)
  2. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  3. Washington State Univ., Pullman, WA (United States)
Publication Date:
OSTI Identifier:
1258488
Report Number(s):
LA-UR--16-20652
Journal ID: ISSN 0020-1669
Grant/Contract Number:
AC52-06NA25396
Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 55; Journal Issue: 10; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Research Org:
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE National Nuclear Security Administration (NNSA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY