Remarkably High Stability of Late Actinide Dioxide Cations: Extending Chemistry to Pentavalent Berkelium and Californium
Abstract
Abstract Actinyl chemistry is extended beyond Cm to BkO 2 + and CfO 2 + through transfer of an O atom from NO 2 to BkO + or CfO + , establishing a surprisingly high lower limit of 73 kcal mol −1 for the dissociation energies, D[O‐(BkO + )] and D[O‐(CfO + )]. CCSD(T) computations are in accord with the observed reactions, and characterize the newly observed dioxide ions as linear pentavalent actinyls; these being the first Bk and Cf species with oxidation states above IV. Computations of actinide dioxide cations AnO 2 + for An=Pa to Lr reveal an unexpected minimum for D[O‐(CmO + )]. For CmO 2 + , and AnO 2 + beyond EsO 2 + , the most stable structure has side‐on bonded η 2 ‐(O 2 ), as An III peroxides for An=Cm and Lr, and as An II superoxides for An=Fm, Md, and No. It is predicted that the most stable structure of EsO 2 + is linear [O=Es V =O] + , einsteinyl, and that FmO 2 + and MdO 2 + , like CmO 2 + , also have actinyl(V) structures as local energy minima. The results expand actinide oxidation state chemistry, the realmmore »
- Authors:
-
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
- Univ. of Alabama, Tuscaloosa, AL (United States). Dept. of Chemistry
- Washington State Univ., Pullman, WA (United States). Dept. of Chemistry
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Nuclear Physics (NP)
- OSTI Identifier:
- 1418310
- Alternate Identifier(s):
- OSTI ID: 1408259
- Grant/Contract Number:
- AC02-05CH11231; FG02-12ER16329
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Chemistry - A European Journal
- Additional Journal Information:
- Journal Volume: 23; Journal Issue: 68; Journal ID: ISSN 0947-6539
- Publisher:
- ChemPubSoc Europe
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; actinides; density functional calculations; gas-phase reactions; redox chemistry; transuranium elements
Citation Formats
Dau, Phuong D., Vasiliu, Monica, Peterson, Kirk A., Dixon, David A., and Gibson, John K.. Remarkably High Stability of Late Actinide Dioxide Cations: Extending Chemistry to Pentavalent Berkelium and Californium. United States: N. p., 2017.
Web. doi:10.1002/chem.201704193.
Dau, Phuong D., Vasiliu, Monica, Peterson, Kirk A., Dixon, David A., & Gibson, John K.. Remarkably High Stability of Late Actinide Dioxide Cations: Extending Chemistry to Pentavalent Berkelium and Californium. United States. https://doi.org/10.1002/chem.201704193
Dau, Phuong D., Vasiliu, Monica, Peterson, Kirk A., Dixon, David A., and Gibson, John K.. Thu .
"Remarkably High Stability of Late Actinide Dioxide Cations: Extending Chemistry to Pentavalent Berkelium and Californium". United States. https://doi.org/10.1002/chem.201704193. https://www.osti.gov/servlets/purl/1418310.
@article{osti_1418310,
title = {Remarkably High Stability of Late Actinide Dioxide Cations: Extending Chemistry to Pentavalent Berkelium and Californium},
author = {Dau, Phuong D. and Vasiliu, Monica and Peterson, Kirk A. and Dixon, David A. and Gibson, John K.},
abstractNote = {Abstract Actinyl chemistry is extended beyond Cm to BkO 2 + and CfO 2 + through transfer of an O atom from NO 2 to BkO + or CfO + , establishing a surprisingly high lower limit of 73 kcal mol −1 for the dissociation energies, D[O‐(BkO + )] and D[O‐(CfO + )]. CCSD(T) computations are in accord with the observed reactions, and characterize the newly observed dioxide ions as linear pentavalent actinyls; these being the first Bk and Cf species with oxidation states above IV. Computations of actinide dioxide cations AnO 2 + for An=Pa to Lr reveal an unexpected minimum for D[O‐(CmO + )]. For CmO 2 + , and AnO 2 + beyond EsO 2 + , the most stable structure has side‐on bonded η 2 ‐(O 2 ), as An III peroxides for An=Cm and Lr, and as An II superoxides for An=Fm, Md, and No. It is predicted that the most stable structure of EsO 2 + is linear [O=Es V =O] + , einsteinyl, and that FmO 2 + and MdO 2 + , like CmO 2 + , also have actinyl(V) structures as local energy minima. The results expand actinide oxidation state chemistry, the realm of the distinctive actinyl moiety, and the non‐periodic character towards the end of the periodic table.},
doi = {10.1002/chem.201704193},
journal = {Chemistry - A European Journal},
number = 68,
volume = 23,
place = {United States},
year = {Thu Oct 12 00:00:00 EDT 2017},
month = {Thu Oct 12 00:00:00 EDT 2017}
}
Web of Science
Works referenced in this record:
Synthesis, Structure, and Reactivity of the Sterically Crowded Th 3+ Complex (C 5 Me 5 ) 3 Th Including Formation of the Thorium Carbonyl, [(C 5 Me 5 ) 3 Th(CO)][BPh 4 ]
journal, February 2017
- Langeslay, Ryan R.; Chen, Guo P.; Windorff, Cory J.
- Journal of the American Chemical Society, Vol. 139, Issue 9
Estimation of effective ion temperatures in a quadrupole ion trap
journal, August 1998
- Gronert, Scott
- Journal of the American Society for Mass Spectrometry, Vol. 9, Issue 8
Oxidation of Gas-Phase Protactinium Ions, Pa + and Pa 2+ : Formation and Properties of PaO 2 2+ (g), Protactinyl
journal, May 2006
- Santos, Marta; Pires de Matos, António; Marçalo, Joaquim
- The Journal of Physical Chemistry A, Vol. 110, Issue 17
Nitrogen dioxide reactions with atomic lanthanide cations and their monoxides: gas-phase kinetics at room temperature
journal, January 2010
- Jarvis, Michael J. Y.; Blagojevic, Voislav; Koyanagi, Gregory K.
- Physical Chemistry Chemical Physics, Vol. 12, Issue 18
Molpro: a general-purpose quantum chemistry program package: Molpro
journal, July 2011
- Werner, Hans-Joachim; Knowles, Peter J.; Knizia, Gerald
- Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 2, Issue 2
Density-functional exchange-energy approximation with correct asymptotic behavior
journal, September 1988
- Becke, A. D.
- Physical Review A, Vol. 38, Issue 6
Covalency hinders AnO 2 (H 2 O) + → AnO(OH) 2 + isomerisation (An = Pa–Pu)
journal, January 2016
- Kaltsoyannis, Nikolas
- Dalton Transactions, Vol. 45, Issue 7
Coupled cluster theory for high spin, open shell reference wave functions
journal, October 1993
- Knowles, Peter J.; Hampel, Claudia; Werner, Hans‐Joachim
- The Journal of Chemical Physics, Vol. 99, Issue 7
A full coupled‐cluster singles and doubles model: The inclusion of disconnected triples
journal, February 1982
- Purvis, George D.; Bartlett, Rodney J.
- The Journal of Chemical Physics, Vol. 76, Issue 4
Organometallic neptunium(III) complexes
journal, May 2016
- Dutkiewicz, Michał S.; Farnaby, Joy H.; Apostolidis, Christos
- Nature Chemistry, Vol. 8, Issue 8
Revision of the Douglas-Kroll transformation
journal, June 1989
- Jansen, Georg; Hess, Bernd A.
- Physical Review A, Vol. 39, Issue 11
Identification of the Formal +2 Oxidation State of Plutonium: Synthesis and Characterization of {Pu II [C 5 H 3 (SiMe 3 ) 2 ] 3 } −
journal, March 2017
- Windorff, Cory J.; Chen, Guo P.; Cross, Justin N.
- Journal of the American Chemical Society, Vol. 139, Issue 11
Extending the Row of Lanthanide Tetrafluorides: A Combined Matrix-Isolation and Quantum-Chemical Study
journal, January 2016
- Vent-Schmidt, Thomas; Fang, Zongtang; Lee, Zachary
- Chemistry - A European Journal, Vol. 22, Issue 7
The heterogeneous hydrolysis of NO2 in laboratory systems and in outdoor and indoor atmospheres: An integrated mechanism
journal, December 2002
- Finlayson-Pitts, B. J.; Wingen, L. M.; Sumner, A. L.
- Physical Chemistry Chemical Physics, Vol. 5, Issue 2
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
Synthesis and Structures of Plutonyl Nitrate Complexes: Is Plutonium Heptavalent in PuO 3 (NO 3 ) 2 – ?
journal, February 2015
- Maurice, Rémi; Renault, Eric; Gong, Yu
- Inorganic Chemistry, Vol. 54, Issue 5
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
Chemistry with ADF
journal, January 2001
- te Velde, G.; Bickelhaupt, F. M.; Baerends, E. J.
- Journal of Computational Chemistry, Vol. 22, Issue 9, p. 931-967
Quantum electrodynamical corrections to the fine structure of helium
journal, January 1974
- Douglas, Marvin; Kroll, Norman M.
- Annals of Physics, Vol. 82, Issue 1
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
A fifth-order perturbation comparison of electron correlation theories
journal, May 1989
- Raghavachari, Krishnan; Trucks, Gary W.; Pople, John A.
- Chemical Physics Letters, Vol. 157, Issue 6
Gas-Phase Energetics of Actinide Oxides: An Assessment of Neutral and Cationic Monoxides and Dioxides from Thorium to Curium †
journal, November 2009
- Marçalo, Joaquim; Gibson, John K.
- The Journal of Physical Chemistry A, Vol. 113, Issue 45
NBO 6.0 : Natural bond orbital analysis program
journal, March 2013
- Glendening, Eric D.; Landis, Clark R.; Weinhold, Frank
- Journal of Computational Chemistry, Vol. 34, Issue 16
Expanding the Chemistry of Molecular U 2+ Complexes: Synthesis, Characterization, and Reactivity of the {[C 5 H 3 (SiMe 3 ) 2 ] 3 U} − Anion
journal, December 2015
- Windorff, Cory J.; MacDonald, Matthew R.; Meihaus, Katie R.
- Chemistry - A European Journal, Vol. 22, Issue 2
Coupled-cluster theory in quantum chemistry
journal, February 2007
- Bartlett, Rodney J.; Musiał, Monika
- Reviews of Modern Physics, Vol. 79, Issue 1
Geometry optimizations in the zero order regular approximation for relativistic effects
journal, May 1999
- van Lenthe, Erik; Ehlers, Andreas; Baerends, Evert-Jan
- The Journal of Chemical Physics, Vol. 110, Issue 18
Intermolecular interactions from a natural bond orbital, donor-acceptor viewpoint
journal, September 1988
- Reed, Alan E.; Curtiss, Larry A.; Weinhold, Frank
- Chemical Reviews, Vol. 88, Issue 6
Electron transfer dissociation of dipositive uranyl and plutonyl coordination complexes: ETD of Uranyl/Plutonyl Complexes
journal, December 2011
- Rios, Daniel; Rutkowski, Philip X.; Shuh, David K.
- Journal of Mass Spectrometry, Vol. 46, Issue 12
Higher Oxidation States of Americium: Preparation, Characterization and Use for Separations
journal, September 2011
- Runde, Wolfgang H.; Mincher, Bruce J.
- Chemical Reviews, Vol. 111, Issue 9
Tutorial on the Role of Cyclopentadienyl Ligands in the Discovery of Molecular Complexes of the Rare-Earth and Actinide Metals in New Oxidation States
journal, September 2016
- Evans, William J.
- Organometallics, Vol. 35, Issue 18
Accurate Relativistic Small-Core Pseudopotentials for Actinides. Energy Adjustment for Uranium and First Applications to Uranium Hydride †
journal, November 2009
- Dolg, Michael; Cao, Xiaoyan
- The Journal of Physical Chemistry A, Vol. 113, Issue 45
Ionization Energies for the Actinide Mono- and Dioxides Series, from Th to Cm: Theory versus Experiment
journal, May 2010
- Infante, Ivan; Kovacs, Attila; Macchia, Giovanni La
- The Journal of Physical Chemistry A, Vol. 114, Issue 19
The electrochemical behavior of cerium(III/IV) complexes: Thermodynamics, kinetics and applications in synthesis
journal, February 2014
- Piro, Nicholas A.; Robinson, Jerome R.; Walsh, Patrick J.
- Coordination Chemistry Reviews, Vol. 260
Perturbative corrections to account for triple excitations in closed and open shell coupled cluster theories
journal, September 1994
- Deegan, Miles J. O.; Knowles, Peter J.
- Chemical Physics Letters, Vol. 227, Issue 3
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
Thermodynamic properties of lanthanide and actinide ions in avueous solution
journal, July 1986
- David, F.
- Journal of the Less Common Metals, Vol. 121
An open-shell spin-restricted coupled cluster method: application to ionization potentials in nitrogen
journal, June 1988
- Rittby, Magnus; Bartlett, Rodney J.
- The Journal of Physical Chemistry, Vol. 92, Issue 11
Gas-Phase Reactions of Atomic Lanthanide Cations with D2O: Room-Temperature Kinetics and Periodicity in Reactivity
journal, August 2006
- Cheng, Ping; Koyanagi, Gregory K.; Bohme, Diethard K.
- ChemPhysChem, Vol. 7, Issue 8
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density
journal, January 1988
- Lee, Chengteh; Yang, Weitao; Parr, Robert G.
- Physical Review B, Vol. 37, Issue 2
Pentavalent Lanthanide Compounds: Formation and Characterization of Praseodymium(V) Oxides
journal, April 2016
- Zhang, Qingnan; Hu, Shu-Xian; Qu, Hui
- Angewandte Chemie, Vol. 128, Issue 24
Gas-Phase Oxidation Reactions of Neptunium and Plutonium Ions Investigated via Fourier Transform Ion Cyclotron Resonance Mass Spectrometry
journal, August 2002
- Santos, Marta; Marçalo, Joaquim; Pires de Matos, António
- The Journal of Physical Chemistry A, Vol. 106, Issue 31
Gas-Phase Uranyl, Neptunyl, and Plutonyl: Hydration and Oxidation Studied by Experiment and Theory
journal, June 2012
- Rios, Daniel; Michelini, Maria C.; Lucena, Ana F.
- Inorganic Chemistry, Vol. 51, Issue 12
Correlation consistent basis sets for actinides. I. The Th and U atoms
journal, February 2015
- Peterson, Kirk A.
- The Journal of Chemical Physics, Vol. 142, Issue 7
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
- Peterson, Kirk A.; Dunning, Thom H.
- The Journal of Chemical Physics, Vol. 117, Issue 23
The zero‐order regular approximation for relativistic effects: The effect of spin–orbit coupling in closed shell molecules
journal, October 1996
- van Lenthe, E.; Snijders, J. G.; Baerends, E. J.
- The Journal of Chemical Physics, Vol. 105, Issue 15
The CeO 2 + Cation: Gas-Phase Reactivity and Electronic Structure
journal, January 1996
- Heinemann, Christoph; Cornehl, Hans H.; Schröder, Detlef
- Inorganic Chemistry, Vol. 35, Issue 9
Oxidation Reactions of Lanthanide Cations with N 2 O and O 2 : Periodicities in Reactivity
journal, October 2001
- Koyanagi, Gregory K.; Bohme, Diethard K.
- The Journal of Physical Chemistry A, Vol. 105, Issue 39
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
- Vasiliu, Monica; Peterson, Kirk A.; Gibson, John K.
- The Journal of Physical Chemistry A, Vol. 119, Issue 46
Correlation consistent basis sets for actinides. II. The atoms Ac and Np–Lr
journal, August 2017
- Feng, Rulin; Peterson, Kirk A.
- The Journal of Chemical Physics, Vol. 147, Issue 8
Relativistic Small-Core Pseudopotentials for Actinium, Thorium, and Protactinium
journal, March 2014
- Weigand, Anna; Cao, Xiaoyan; Hangele, Tim
- The Journal of Physical Chemistry A, Vol. 118, Issue 13
The generalized Douglas–Kroll transformation
journal, November 2002
- Wolf, Alexander; Reiher, Markus; Hess, Bernd Artur
- The Journal of Chemical Physics, Vol. 117, Issue 20
Parallel Douglas–Kroll energy and gradients in NWChem: Estimating scalar relativistic effects using Douglas–Kroll contracted basis sets
journal, January 2001
- de Jong, W. A.; Harrison, R. J.; Dixon, D. A.
- The Journal of Chemical Physics, Vol. 114, Issue 1
Pentavalent Lanthanide Compounds: Formation and Characterization of Praseodymium(V) Oxides
journal, April 2016
- Zhang, Qingnan; Hu, Shu-Xian; Qu, Hui
- Angewandte Chemie International Edition, Vol. 55, Issue 24
Identification of an iridium-containing compound with a formal oxidation state of IX
journal, October 2014
- Wang, Guanjun; Zhou, Mingfei; Goettel, James T.
- Nature, Vol. 514, Issue 7523
Electronic Structure and Bonding in Actinyl Ions and their Analogs
journal, May 2007
- Denning, Robert G.
- The Journal of Physical Chemistry A, Vol. 111, Issue 20
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
- Watts, John D.; Gauss, Jürgen; Bartlett, Rodney J.
- The Journal of Chemical Physics, Vol. 98, Issue 11
FTICR-MS study of the gas-phase thermochemistry of americium oxides
journal, August 2003
- Santos, Marta; Marçalo, Joaquim; Leal, João Paulo
- International Journal of Mass Spectrometry, Vol. 228, Issue 2-3
Relativistic regular two‐component Hamiltonians
journal, September 1993
- Lenthe, E. van; Baerends, E. J.; Snijders, J. G.
- The Journal of Chemical Physics, Vol. 99, Issue 6
Relativistic total energy using regular approximations
journal, December 1994
- van Lenthe, E.; Baerends, E. J.; Snijders, J. G.
- The Journal of Chemical Physics, Vol. 101, Issue 11
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
Segmented contraction scheme for small-core actinide pseudopotential basis sets
journal, March 2004
- Cao, Xiaoyan; Dolg, Michael
- Journal of Molecular Structure: THEOCHEM, Vol. 673, Issue 1-3
Gas-Phase Oxidation of Cm + and Cm 2+ − Thermodynamics of Neutral and Ionized CmO
journal, November 2008
- Gibson, John K.; Haire, Richard G.; Santos, Marta
- The Journal of Physical Chemistry A, Vol. 112, Issue 45
Relativistic regular two-component Hamiltonians
journal, February 1996
- van Lenthe, E.; van Leeuwen, R.; Baerends, E. J.
- International Journal of Quantum Chemistry, Vol. 57, Issue 3