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

Abstract

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:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Washington State Univ., Pullman, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1258488
Alternate Identifier(s):
OSTI ID: 1596311
Report Number(s):
LA-UR-16-20652
Journal ID: ISSN 0020-1669
Grant/Contract Number:  
AC52-06NA25396; SC0001815
Resource 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)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Kelley, Morgan P., Yang, Ping, Clark, Sue B., and Clark, Aurora E. Structural and thermodynamic properties of the CmIII ion solvated by water and methanol. United States: N. p., 2016. Web. doi:10.1021/acs.inorgchem.6b00477.
Kelley, Morgan P., Yang, Ping, Clark, Sue B., & Clark, Aurora E. Structural and thermodynamic properties of the CmIII ion solvated by water and methanol. United States. doi:10.1021/acs.inorgchem.6b00477.
Kelley, Morgan P., Yang, Ping, Clark, Sue B., and Clark, Aurora E. Wed . "Structural and thermodynamic properties of the CmIII ion solvated by water and methanol". United States. doi:10.1021/acs.inorgchem.6b00477. https://www.osti.gov/servlets/purl/1258488.
@article{osti_1258488,
title = {Structural and thermodynamic properties of the CmIII ion solvated by water and methanol},
author = {Kelley, Morgan P. and Yang, Ping and Clark, Sue B. and Clark, Aurora E.},
abstractNote = {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.},
doi = {10.1021/acs.inorgchem.6b00477},
journal = {Inorganic Chemistry},
number = 10,
volume = 55,
place = {United States},
year = {2016},
month = {4}
}

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