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Title: Reliable Potential Energy Surfaces for the Reactions of H2O with ThO2, PaO2+, UO22+, and UO2+

Journal Article · · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
 [1];  [2];  [3];  [1]
  1. Univ. of Alabama, Tuscaloosa, AL (United States). Dept. of Chemistry
  2. Washington State Univ., Pullman, WA (United States). Dept. of Chemistry
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
+ Show Author Affiliations

The potential energy surfaces for the reactions of H2O with ThO2, PaO2+, UO22+, and UO2+ have been calculated at the coupled cluster CCSD(T) level extrapolated to the complete basis set limit with additional corrections including scalar relativistic and spin-orbit. The reactions proceed by the formation of an initial Lewis acid-base adduct (H2O)AnO20/+/2+ followed by a proton transfer to generate the dihydroxide AnO(OH)20/+/2+. The results are in excellent agreement with mass spectrometry experiments and prior calculations of hydrolysis reactions of the group 4 transition metal dioxides MO2. The differences in the energies of the stationary points on the potential energy surface are explained in terms of the charges on the system and the populations on the metal center. The use of an improved starting point for the coupled cluster CCSD(T) calculations based on density functional theory with the PW91 exchange-correlation functional or Brueckner orbitals is described. The importance of including second-order spin-orbit corrections for closed-shell molecules is also described. These improvements in the calculations are then correlated with the 5f populations on the actinide.

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
Grant/Contract Number:
AC02-05CH11231; FG02-12ER16329
OSTI ID:
1461097
Journal Information:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Vol. 119, Issue 46; Related Information: © 2015 American Chemical Society.; ISSN 1089-5639
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 52 works
Citation information provided by
Web of Science

References (59)

The Formula of Uranyl Ion journal July 1949
The uranium(V)-catalysed exchange reaction between uranyl ion and water in perchloric acid solution journal February 1961
Chemical Speciation of the Uranyl Ion under Highly Alkaline Conditions. Synthesis, Structures, and Oxo Ligand Exchange Dynamics journal April 1999
Reactivity of the “yl”-Bond in Uranyl(VI) Complexes. 1. Rates and Mechanisms for the Exchange between the trans -dioxo Oxygen Atoms in (UO 2 ) 2 (OH) 2 2+ and Mononuclear UO 2 (OH) n 2- n Complexes with Solvent Water journal October 2007
On the Mechanism of Oxygen Exchange Between Uranyl(VI) Oxygen and Water in Strongly Alkaline Solution as Studied by 17 O NMR Magnetization Transfer journal June 2010
Oxo ligand functionalization in the uranyl ion (UO22+) journal February 2010
An Investigation of the Accuracy of Different DFT Functionals on the Water Exchange Reaction in Hydrated Uranyl(VI) in the Ground State and the First Excited State journal February 2008
Ab Initio Study of the Mechanism for Photoinduced Yl-Oxygen Exchange in Uranyl(VI) in Acidic Aqueous Solution journal September 2008
Theoretical Study of the Oxygen Exchange in Uranyl Hydroxide. An Old Riddle Solved? journal October 2008
Theoretical Actinide Molecular Science journal January 2010
Oxygen Exchange in Uranyl Hydroxide via Two “Nonclassical” Ions journal April 2010
Insights into Uranyl Chemistry from Molecular Dynamics Simulations journal September 2011
“yl”-Oxygen Exchange in Uranyl(VI) Ion: A Mechanism Involving (UO 2 ) 2 (μ-OH) 2 2+ via U–O yl –U Bridge Formation journal January 2012
OXYGEN EXCHANGE REACTIONS OF PLUTONIUM IONS IN SOLUTION 1 journal February 1963
THE OXYGEN EXCHANGE REACTIONS OF NpO 2 +2 AND NpO 2 + WITH WATER 1 journal December 1963
On the Origins of Faster Oxo Exchange for Uranyl(V) versus Plutonyl(V) journal September 2012
Elucidating Protactinium Hydrolysis: The Relative Stabilities of PaO 2 (H 2 O) + and PaO(OH) 2 + journal July 2015
Computational Study of H 2 and O 2 Production from Water Splitting by Small (MO 2 ) n Clusters (M = Ti, Zr, Hf) journal April 2013
Computational Study of the Hydrolysis Reactions of Small MO 2 (M = Zr and Hf) Nanoclusters with Water journal April 2012
Computational Study of the Hydrolysis Reactions of the Ground and First Excited Triplet States of Small TiO 2 Nanoclusters journal April 2011
Correlation consistent basis sets for actinides. I. The Th and U atoms journal February 2015
A full coupled‐cluster singles and doubles model: The inclusion of disconnected triples journal February 1982
A fifth-order perturbation comparison of electron correlation theories journal May 1989
Coupled‐cluster methods with noniterative triple excitations for restricted open‐shell Hartree–Fock and other general single determinant reference functions. Energies and analytical gradients journal June 1993
Coupled-cluster theory in quantum chemistry journal February 2007
Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen journal January 1989
Electron affinities of the first‐row atoms revisited. Systematic basis sets and wave functions journal May 1992
Accurate Relativistic Small-Core Pseudopotentials for Actinides. Energy Adjustment for Uranium and First Applications to Uranium Hydride † journal November 2009
Relativistic Small-Core Pseudopotentials for Actinium, Thorium, and Protactinium journal March 2014
Accurate correlation consistent basis sets for molecular core–valence correlation effects: The second row atoms Al–Ar, and the first row atoms B–Ne revisited journal December 2002
Note on an Approximation Treatment for Many-Electron Systems journal October 1934
Theoretical models incorporating electron correlation journal January 1976
Perturbative corrections to account for triple excitations in closed and open shell coupled cluster theories journal September 1994
An open-shell spin-restricted coupled cluster method: application to ionization potentials in nitrogen journal June 1988
Coupled cluster theory for high spin, open shell reference wave functions journal October 1993
Benchmark calculations with correlated molecular wave functions. IV. The classical barrier height of the H+H 2 →H 2 +H reaction journal May 1994
Quantum electrodynamical corrections to the fine structure of helium journal January 1974
The generalized Douglas–Kroll transformation journal November 2002
Parallel Douglas–Kroll energy and gradients in NWChem: Estimating scalar relativistic effects using Douglas–Kroll contracted basis sets journal January 2001
An infinite-order two-component relativistic Hamiltonian by a simple one-step transformation journal February 2007
Relativistic Hamiltonians for Chemistry: A Primer journal November 2011
Formulation and implementation of a relativistic unrestricted coupled‐cluster method including noniterative connected triples journal November 1996
Formulation and implementation of the relativistic Fock-space coupled cluster method for molecules journal December 2001
Molpro: a general-purpose quantum chemistry program package: Molpro
  • Werner, Hans-Joachim; Knowles, Peter J.; Knizia, Gerald
  • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 2, Issue 2 https://doi.org/10.1002/wcms.82
journal July 2011
Accurate and simple analytic representation of the electron-gas correlation energy journal June 1992
Generalized gradient approximation for the exchange-correlation hole of a many-electron system journal December 1996
Nuclear Saturation and Two-Body Forces. II. Tensor Forces journal October 1954
Analysis of the S 2 Ground State of Lithium in Terms of Natural and Best Overlap (Brueckner) Spin Orbitals with Implications for the Fermi Contact Term journal February 1969
An electron pair operator approach to coupled cluster wave functions. Application to He 2 , Be 2 , and Mg 2 and comparison with CEPA methods journal April 1981
An examination of the Brueckner condition for the selection of molecular orbitals in correlated wavefunctions journal February 1977
Size-consistent Brueckner theory limited to double substitutions journal December 1989
Actinide Dioxides in Water: Interactions at the Interface journal November 2011
Gas Phase Properties of MX 2 and MX 4 (X = F, Cl) for M = Group 4, Group 14, Cerium, and Thorium journal May 2015
Gas-Phase Energetics of Actinide Oxides: An Assessment of Neutral and Cationic Monoxides and Dioxides from Thorium to Curium † journal November 2009
Accurate Thermochemistry for Transition Metal Oxide Clusters journal July 2009
Comprehensive Handbook of Chemical Bond Energies book March 2007
Intermolecular interactions from a natural bond orbital, donor-acceptor viewpoint journal September 1988
NBO 6.0 : Natural bond orbital analysis program journal March 2013
Oxo-Exchange of Gas-Phase Uranyl, Neptunyl, and Plutonyl with Water and Methanol journal December 2013

Cited By (12)

Infrared Spectra of the HAnX and H 2 AnX 2 Molecules (An=Th and U, X=Cl and Br) in Argon Matrices Supported by Electronic Structure Calculations journal January 2019
Bond energy of ThN + : A guided ion beam and quantum chemical investigation of the reactions of thorium cation with N 2 and NO journal July 2019
Remarkably High Stability of Late Actinide Dioxide Cations: Extending Chemistry to Pentavalent Berkelium and Californium journal November 2017
Gas Phase Hydrolysis and Oxo‐Exchange of Actinide Dioxide Cations: Elucidating Intrinsic Chemistry from Protactinium to Einsteinium journal January 2019
Covalency hinders AnO 2 (H 2 O) + → AnO(OH) 2 + isomerisation (An = Pa–Pu) journal January 2016
Mononuclear thorium halide clusters ThX 4 (X = F, Cl): gas-phase hydrolysis reactions journal January 2018
Protactinium and the intersection of actinide and transition metal chemistry journal February 2018
Correlation consistent basis sets for lanthanides: The atoms La–Lu journal August 2016
Formation and hydrolysis of gas-phase [UO 2 (R)] + : R═CH 3 , CH 2 CH 3 , CH═CH 2 , and C 6 H 5 journal September 2019
Correlation consistent basis sets for actinides. II. The atoms Ac and Np–Lr journal August 2017
Bond energies of ThO + and ThC + : A guided ion beam and quantum chemical investigation of the reactions of thorium cation with O 2 and CO journal May 2016
Protactinium And The Intersection Of Actinide And Transition Metal Chemistry text January 2018

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
actinyl reactions
coupled cluster CCSD(T)
relativistic quantum chemistry
hydrolysis