Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

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. 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]
+ Show Author Affiliations
  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 Laboratory (LANL), Los Alamos, NM (United States); Washington State Univ., Pullman, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); 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.
Copy to clipboard
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. https://doi.org/10.1021/acs.inorgchem.6b00477
Copy to clipboard
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. https://doi.org/10.1021/acs.inorgchem.6b00477. https://www.osti.gov/servlets/purl/1258488.
Copy to clipboard
@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. 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 = {Wed Apr 27 00:00:00 EDT 2016},
month = {Wed Apr 27 00:00:00 EDT 2016}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/acs.inorgchem.6b00477
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 10 works
Citation information provided by
Web of Science
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

Impact limits of partitioning and transmutation scenarios on the radiotoxicity of actinides in radioactive waste
journal, October 2003

Optical properties of Cm(III) in crystals and solutions and their application to Cm(III) speciation
journal, April 2006

  • Edelstein, Norman M.; Klenza, Reinhardt; Fanghanel, Thomas
  • Coordination Chemistry Reviews, Vol. 250, Issue 7-8, p. 948-973
  • DOI: 10.1016/j.ccr.2006.02.004

The Curium Aqua Ion
journal, April 2007

  • Skanthakumar, S.; Antonio, Mark R.; Wilson, Richard E.
  • Inorganic Chemistry, Vol. 46, Issue 9
  • DOI: 10.1021/ic061798b

A Quantum Chemical and Molecular Dynamics Study of the Coordination of Cm(III) in Water
journal, November 2007

  • Hagberg, Daniel; Bednarz, Eugeniusz; Edelstein, Norman M.
  • Journal of the American Chemical Society, Vol. 129, Issue 46
  • DOI: 10.1021/ja075489b

Chemical Speciation of Trivalent Actinides and Lanthanides in Biological Fluids: The Dominant in Vitro Binding Form of Curium(III) and Europium(III) in Human Urine
journal, February 2011

  • Heller, Anne; Barkleit, Astrid; Bernhard, Gert
  • Chemical Research in Toxicology, Vol. 24, Issue 2
  • DOI: 10.1021/tx100273g

Self-diffusion coefficients of the trivalent f-element ion series in dilute and moderately dilute aqueous solutions: A comparative study between europium, gadolinium, terbium and berkelium
journal, March 2010

  • Rafik, Besbes; Noureddine, Ouerfelli; Abderabbou, Abdelmanef
  • IOP Conference Series: Materials Science and Engineering, Vol. 9
  • DOI: 10.1088/1757-899X/9/1/012079

Curium(III) species and the coordination states in concentrated LiCl-aqueous solutions studied by time-resolved laser-induced fluorescence spectroscopy
journal, February 2006

Aqueous curium(III) phosphate species characterized by time-resolved laser-induced fluorescence spectroscopy
journal, August 2011

Circularly Polarized Luminescence of Curium: A New Characterization of the 5f Actinide Complexes
journal, September 2012

  • Law, Ga-Lai; Andolina, Christopher M.; Xu, Jide
  • Journal of the American Chemical Society, Vol. 134, Issue 37
  • DOI: 10.1021/ja306354n

f-State luminescence of trivalent lanthanide and actinide ions in solution
journal, June 1994

Luminescence study on determination of the hydration number of Cm(III)
journal, October 1994

On the electronic structure of Cm(H2O)n3+ (n=1,2,4,6) by all-electron Dirac–Hartree–Fock calculations
journal, May 2002

  • Mochizuki, Yuji; Tatewaki, Hiroshi
  • The Journal of Chemical Physics, Vol. 116, Issue 20
  • DOI: 10.1063/1.1473803

Approaching actinide(+III) hydration from first principles
journal, January 2007

  • Wiebke, J.; Moritz, A.; Cao, X.
  • Phys. Chem. Chem. Phys., Vol. 9, Issue 4
  • DOI: 10.1039/B614092K

Hydration Shell Structure and Dynamics of Curium(III) in Aqueous Solution: First Principles and Empirical Studies
journal, May 2011

  • Atta-Fynn, Raymond; Bylaska, Eric J.; Schenter, Gregory K.
  • The Journal of Physical Chemistry A, Vol. 115, Issue 18
  • DOI: 10.1021/jp201043f

Importance of Counteranions on the Hydration Structure of the Curium Ion
journal, June 2013

  • Atta-Fynn, Raymond; Bylaska, Eric J.; de Jong, Wibe A.
  • The Journal of Physical Chemistry Letters, Vol. 4, Issue 13
  • DOI: 10.1021/jz400887a

From ions in solution to ions in the gas phase - the mechanism of electrospray mass spectrometry
journal, November 1993

Enhancement of retention by ion-pair formation in liquid chromatography with nonpolar stationary phases
journal, December 1977

  • Horvath, Csaba.; Melander, Wayne.; Molnar, Imre.
  • Analytical Chemistry, Vol. 49, Issue 14
  • DOI: 10.1021/ac50022a048

Electrophoretic mobilities of cationic analytes in non-aqueous methanol, acetonitrile and their mixtures
journal, July 2001

A TRLFS Study on the Complexation of CmIII and EuIII with 2,6-Bis(5,6-dipropyl-1,2,4-triazin-3-yl)pyridine in Water/Methanol Mixture
journal, May 2010

  • Trumm, Sascha; Panak, Petra J.; Geist, Andreas
  • European Journal of Inorganic Chemistry, Vol. 2010, Issue 19
  • DOI: 10.1002/ejic.201000230

Enthalpies and Entropies of Transfer of Electrolytes and Ions from Water to Mixed Aqueous Organic Solvents
journal, August 2002

  • Hefter, Glenn; Marcus, Yizhak; Waghorne, W. Earle
  • Chemical Reviews, Vol. 102, Issue 8
  • DOI: 10.1021/cr010031s

Ion-solvent interaction. VI. Thermodynamic approach to preferential solvation in mixed solvents
journal, March 1968

Preferential solvation of ions in mixed solvents. Part 2.—The solvent composition near the ion
journal, January 1988

  • Marcus, Yizhak
  • Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 84, Issue 5
  • DOI: 10.1039/f19888401465

Preferential solvation. Part 3.—Binary solvent mixtures
journal, January 1989

  • Marcus, Yizhak
  • Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 85, Issue 2
  • DOI: 10.1039/f19898500381

Preferential solvation of ions in mixed solvents. Part 4.—Comparison of the Kirkwood–Buff and quasi-lattice quasi-chemical approaches
journal, January 1989

  • Marcus, Yizhak
  • Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 85, Issue 9
  • DOI: 10.1039/f19898503019

Ion Pairing
journal, November 2006

  • Marcus, Yizhak; Hefter, Glenn
  • Chemical Reviews, Vol. 106, Issue 11
  • DOI: 10.1021/cr040087x

Ions in Solution and their Solvation
book, June 2015

Preferential solvation of ions in mixed solvents. Part 4.—Preferential solvation of Cu+ in acetone + acetonitrile and N,N-dimethylacetamide + acetonitrile mixtures using conductance measurements
journal, January 1985

  • Gill, Dip Singh; Kumari, Neena; Chauhan, Mohinder Singh
  • Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 81, Issue 3
  • DOI: 10.1039/f19858100687

Ion solvation dynamics in water–methanol and water– dimethylsulfoxide mixtures
journal, June 1999

  • Day, Tyler J. F.; Patey, G. N.
  • The Journal of Chemical Physics, Vol. 110, Issue 22
  • DOI: 10.1063/1.479030

Density‐functional thermochemistry. III. The role of exact exchange
journal, April 1993

  • Becke, Axel D.
  • The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652
  • DOI: 10.1063/1.464913

Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density
journal, January 1988

Electron affinities of the first‐row atoms revisited. Systematic basis sets and wave functions
journal, May 1992

  • Kendall, Rick A.; Dunning, Thom H.; Harrison, Robert J.
  • The Journal of Chemical Physics, Vol. 96, Issue 9
  • DOI: 10.1063/1.462569

Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen
journal, January 1989

  • Dunning, Thom H.
  • The Journal of Chemical Physics, Vol. 90, Issue 2
  • DOI: 10.1063/1.456153

Energy‐adjusted pseudopotentials for the actinides. Parameter sets and test calculations for thorium and thorium monoxide
journal, May 1994

  • Küchle, W.; Dolg, M.; Stoll, H.
  • The Journal of Chemical Physics, Vol. 100, Issue 10
  • DOI: 10.1063/1.466847

Valence basis sets for relativistic energy-consistent small-core actinide pseudopotentials
journal, January 2003

  • Cao, Xiaoyan; Dolg, Michael; Stoll, Hermann
  • The Journal of Chemical Physics, Vol. 118, Issue 2
  • DOI: 10.1063/1.1521431

MP2 energy evaluation by direct methods
journal, December 1988

Note on an Approximation Treatment for Many-Electron Systems
journal, October 1934

Natural population analysis
journal, July 1985

  • Reed, Alan E.; Weinstock, Robert B.; Weinhold, Frank
  • The Journal of Chemical Physics, Vol. 83, Issue 2
  • DOI: 10.1063/1.449486

Unified Approach for Molecular Dynamics and Density-Functional Theory
journal, November 1985

NWChem: A comprehensive and scalable open-source solution for large scale molecular simulations
journal, September 2010

  • Valiev, M.; Bylaska, E. J.; Govind, N.
  • Computer Physics Communications, Vol. 181, Issue 9, p. 1477-1489
  • DOI: 10.1016/j.cpc.2010.04.018

PACKMOL: A package for building initial configurations for molecular dynamics simulations
journal, October 2009

  • Martínez, L.; Andrade, R.; Birgin, E. G.
  • Journal of Computational Chemistry, Vol. 30, Issue 13
  • DOI: 10.1002/jcc.21224

Methods of conjugate gradients for solving linear systems
journal, December 1952

  • Hestenes, M. R.; Stiefel, E.
  • Journal of Research of the National Bureau of Standards, Vol. 49, Issue 6
  • DOI: 10.6028/jres.049.044

Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Efficient pseudopotentials for plane-wave calculations
journal, January 1991

A unified formulation of the constant temperature molecular dynamics methods
journal, July 1984

  • Nosé, Shuichi
  • The Journal of Chemical Physics, Vol. 81, Issue 1
  • DOI: 10.1063/1.447334

Canonical dynamics: Equilibrium phase-space distributions
journal, March 1985

ChemNetworks: A complex network analysis tool for chemical systems
journal, December 2013

  • Ozkanlar, Abdullah; Clark, Aurora E.
  • Journal of Computational Chemistry, Vol. 35, Issue 6
  • DOI: 10.1002/jcc.23506

Novel Analysis of Cation Solvation Using a Graph Theoretic Approach
journal, March 2012

  • Mooney, Barbara Logan; Corrales, L. Rene; Clark, Aurora E.
  • The Journal of Physical Chemistry B, Vol. 116, Issue 14
  • DOI: 10.1021/jp300193j

Determining polyhedral arrangements of atoms using PageRank
journal, June 2012

  • Hudelson, Matthew; Mooney, Barbara Logan; Clark, Aurora E.
  • Journal of Mathematical Chemistry, Vol. 50, Issue 9
  • DOI: 10.1007/s10910-012-0033-7

MoleculaRnetworks: An integrated graph theoretic and data mining tool to explore solvent organization in molecular simulation
journal, January 2012

  • Mooney, Barbara Logan; Corrales, L. René; Clark, Aurora E.
  • Journal of Computational Chemistry, Vol. 33, Issue 8
  • DOI: 10.1002/jcc.22917

Trends in Aqueous Hydration Across the 4f Period Assessed by Reliable Computational Methods
journal, September 2010

  • Kuta, Jadwiga; Clark, Aurora E.
  • Inorganic Chemistry, Vol. 49, Issue 17
  • DOI: 10.1021/ic100623y

Density Functional Theory Studies of the Electronic Structure of Solid State Actinide Oxides
journal, October 2012

  • Wen, Xiao-Dong; Martin, Richard L.; Henderson, Thomas M.
  • Chemical Reviews, Vol. 113, Issue 2
  • DOI: 10.1021/cr300374y

Covalency in f-element complexes
journal, January 2013

  • Neidig, Michael L.; Clark, David L.; Martin, Richard L.
  • Coordination Chemistry Reviews, Vol. 257, Issue 2
  • DOI: 10.1016/j.ccr.2012.04.029

Thermodynamic and Structural Features of Aqueous Ce(III)
journal, November 2008

  • Dinescu, Adriana; Clark, Aurora E.
  • The Journal of Physical Chemistry A, Vol. 112, Issue 44
  • DOI: 10.1021/jp8076408

Structure and Dynamics of NaCl Ion Pairing in Solutions of Water and Methanol
journal, December 2015

  • Kelley, Morgan; Donley, Amber; Clark, Sue
  • The Journal of Physical Chemistry B, Vol. 119, Issue 51
  • DOI: 10.1021/acs.jpcb.5b07492
    Sort by:
    [ × clear filter / sort ]

    Works referencing / citing this record:

    Spectroscopic and Computational Characterization of Diethylenetriaminepentaacetic Acid/Transplutonium Chelates: Evidencing Heterogeneity in the Heavy Actinide(III) Series
    journal, March 2018

    • Deblonde, Gauthier J. -P.; Kelley, Morgan P.; Su, Jing
    • Angewandte Chemie International Edition, Vol. 57, Issue 17
    • DOI: 10.1002/anie.201709183

    Binding affinity of pyridines with Am III /Cm III elucidated by density functional theory calculations
    journal, January 2019

    • Yu, Jie; Ma, Jun; Yang, Chuting
    • Dalton Transactions, Vol. 48, Issue 5
    • DOI: 10.1039/c8dt04669g

    PageRank as a collective variable to study complex chemical transformations and their energy landscapes
    journal, April 2019

    • Zhou, Tiecheng; Martinez-Baez, Ernesto; Schenter, Gregory
    • The Journal of Chemical Physics, Vol. 150, Issue 13
    • DOI: 10.1063/1.5082648
      Sort by:
      [ × clear filter / sort ]

      Similar Records in DOE PAGES and OSTI.GOV collections: