skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Gas Phase Hydrolysis and Oxo-Exchange of Actinide Dioxide Cations: Elucidating Intrinsic Chemistry from Protactinium to Einsteinium

Journal Article · · Chemistry - A European Journal
 [1]; ORCiD logo [2];  [3];  [1]
  1. Univ. of Alabama, Tuscaloosa, AL (United States)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  3. Washington State Univ., Pullman, WA (United States)
+ Show Author Affiliations

Gas-phase bimolecular reactions of metal cations with water provide insights into intrinsic characteristics of hydrolysis. For the actinide dioxide cations, actinyl(V) AnO2+, melding of experiment and computation provides insights into trends for hydrolysis, as well as for oxo-exchange between actinyls and water that proceeds by a hydrolysis pathway. Here this line of inquiry is further extended into the actinide series with CCSD(T) computations of potential energy surfaces, for the reaction pathway for oxo-exchange through hydrolysis of nine actinyl(V) ions, from PaO2+ to EsO2+. The computed surfaces are in accord with previous experimental results for oxo-exchange, and furthermore predict spontaneous exchange for CmO2+, BkO2+, CfO2+ and EsO2+, but not for AmO2+. Natural Bond Order analysis of the species involved in both hydrolysis and oxo-exchange reveals an inverse correlation between the barrier to hydrolysis and the charge on the actinide centre, q(An). Based on this correlation, it can be concluded that hydrolysis, and related phenomena such as oxo-exchange, become less favourable as the charge on the metal centre decreases. Finally, the new results provide a straightforward rationalization of trends across a wide swathe of the actinide series.

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Washington State Univ., Pullman, WA (United States); Univ. of Alabama, Tuscaloosa, AL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-05CH11231; FG02-12ER16329; SC0018921; AC02-05-CH11231; SC0008501
OSTI ID:
1631602
Alternate ID(s):
OSTI ID: 1490903; OSTI ID: 1657538
Journal Information:
Chemistry - A European Journal, Vol. 25, Issue 17; ISSN 0947-6539
Publisher:
ChemPubSoc EuropeCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 14 works
Citation information provided by
Web of Science

References (51)

Theoretical Study of the Oxygen Exchange in Uranyl Hydroxide. An Old Riddle Solved? journal October 2008
Remarkably High Stability of Late Actinide Dioxide Cations: Extending Chemistry to Pentavalent Berkelium and Californium journal November 2017
A Correlation of Reaction Rates journal January 1955
“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
Elucidating Protactinium Hydrolysis: The Relative Stabilities of PaO 2 (H 2 O) + and PaO(OH) 2 + journal July 2015
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
Covalency hinders AnO 2 (H 2 O) + → AnO(OH) 2 + isomerisation (An = Pa–Pu) journal January 2016
Coupled cluster theory for high spin, open shell reference wave functions journal October 1993
Computational Study of the Hydrolysis Reactions of the Ground and First Excited Triplet States of Small TiO 2 Nanoclusters journal April 2011
A full coupled‐cluster singles and doubles model: The inclusion of disconnected triples journal February 1982
Revision of the Douglas-Kroll transformation journal June 1989
Energy‐adjusted pseudopotentials for the actinides. Parameter sets and test calculations for thorium and thorium monoxide journal May 1994
Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen journal January 1989
The Formula of Uranyl Ion journal July 1949
Quantum electrodynamical corrections to the fine structure of helium journal January 1974
Electron affinities of the first‐row atoms revisited. Systematic basis sets and wave functions journal May 1992
OXYGEN EXCHANGE REACTIONS OF PLUTONIUM IONS IN SOLUTION 1 journal February 1963
NBO 6.0 : Natural bond orbital analysis program journal March 2013
The uranium(V)-catalysed exchange reaction between uranyl ion and water in perchloric acid solution journal February 1961
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
Coupled-cluster theory in quantum chemistry journal February 2007
Prediction of Bond Dissociation Energies/Heats of Formation for Diatomic Transition Metal Compounds: CCSD(T) Works journal January 2017
Intermolecular interactions from a natural bond orbital, donor-acceptor viewpoint journal September 1988
Accurate Relativistic Small-Core Pseudopotentials for Actinides. Energy Adjustment for Uranium and First Applications to Uranium Hydride † journal November 2009
Perturbative corrections to account for triple excitations in closed and open shell coupled cluster theories journal September 1994
Density‐functional thermochemistry. III. The role of exact exchange journal April 1993
Oxygen Exchange in Uranyl Hydroxide via Two “Nonclassical” Ions journal April 2010
Generalized gradient approximation for the exchange-correlation hole of a many-electron system journal December 1996
Theoretical Actinide Molecular Science journal January 2010
An open-shell spin-restricted coupled cluster method: application to ionization potentials in nitrogen journal June 1988
Insights into Uranyl Chemistry from Molecular Dynamics Simulations journal September 2011
Ab Initio Study of the Mechanism for Photoinduced Yl-Oxygen Exchange in Uranyl(VI) in Acidic Aqueous Solution journal September 2008
Benchmark Calculations of Energetic Properties of Groups 4 and 6 Transition Metal Oxide Nanoclusters Including Comparison to Density Functional Theory journal July 2016
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
THE OXYGEN EXCHANGE REACTIONS OF NpO 2 +2 AND NpO 2 + WITH WATER 1 journal December 1963
Oxo ligand functionalization in the uranyl ion (UO22+) journal February 2010
Correlation consistent basis sets for actinides. I. The Th and U atoms journal February 2015
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
Accurate and simple analytic representation of the electron-gas correlation energy journal June 1992
Reliable Potential Energy Surfaces for the Reactions of H 2 O with ThO 2 , PaO 2 + , UO 2 2+ , and UO 2 + journal November 2015
Correlation consistent basis sets for actinides. II. The atoms Ac and Np–Lr journal August 2017
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
Relativistic Small-Core Pseudopotentials for Actinium, Thorium, and Protactinium journal March 2014
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
Computational Study of the Hydrolysis Reactions of Small MO 2 (M = Zr and Hf) Nanoclusters with Water journal April 2012
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
Derivation of a Generalized Gradient Approximation: The PW91 Density Functional book January 1998
Chemical Speciation of the Uranyl Ion under Highly Alkaline Conditions. Synthesis, Structures, and Oxo Ligand Exchange Dynamics journal April 1999
On the Origins of Faster Oxo Exchange for Uranyl(V) versus Plutonyl(V) journal September 2012
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density text January 1988

Figures / Tables (15)

Figure 1(p. 4)figure Figure 1
Scheme 1(p. 6)figure Scheme 1
Figure 2(p. 7)figure Figure 2
Scheme 2(p. 7)figure Scheme 2
Table 1(p. 7)table Table 1
Table 1 (Continued)(p. 8)table Table 1 (Continued)
Table 2(p. 10)table Table 2
Figure 3(p. 11)figure Figure 3
Table 3(p. 12)table Table 3
Figure 4(p. 13)figure Figure 4
Figure 5(p. 14)figure Figure 5
Figure 6(p. 14)figure Figure 6
Figure 7(p. 15)figure Figure 7
Figure 8(p. 16)figure Figure 8
Figure 9(p. 19)figure Figure 9

Similar Records

Remarkably High Stability of Late Actinide Dioxide Cations: Extending Chemistry to Pentavalent Berkelium and Californium
Journal Article · Thu Oct 12 00:00:00 EDT 2017 · Chemistry - A European Journal · OSTI ID:1631602
+2 more
Activation of Water by Pentavalent Actinide Dioxide Cations: Characteristic Curium Revealed by a Reactivity Turn after Americium
Journal Article · Thu Sep 26 00:00:00 EDT 2019 · Inorganic Chemistry · OSTI ID:1631602
+4 more
A Computational Assessment of Actinide Dioxide Cations AnO22+ for An = U to Lr: The Limited Stability Range of the Hexavalent Actinyl Moiety, [O=An=O]2+
Journal Article · Thu Mar 26 00:00:00 EDT 2020 · Inorganic Chemistry · OSTI ID:1631602
+2 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
actinides
computational chemistry
ion-molecule reactions
reaction mechanisms
transuranium elements