Skip to main content
OSTI.GOVU.S. Department of Energy Office of Scientific and Technical Information
U.S. Department of Energy
Office of Scientific and Technical Information
 

Pentavalent Curium, Berkelium, and Californium in Nitrate Complexes: Extending Actinide Chemistry and Oxidation States

Journal Article · · Inorganic Chemistry
 [1];  [2];  [3];  [2]
  1. European Commission, Karlsruhe (Germany). Joint Research Centre
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  3. Universidade de Lisboa, Lisbon (Portugal). Inst. of Superior Tecnico (IST)
+ Show Author Affiliations

Pentavalent actinyl nitrate complexes AnVO2(NO3)2- were produced by elimination of two NO2 from AnIII(NO3)4- for An = Pu, Am, Cm, Bk, and Cf. Density functional theory (B3LYP) and relativistic multireference (CASPT2) calculations confirmed the AnO2(NO3)2- as AnVO2+ actinyl moieties coordinated by nitrates. Computations of alternative AnIIIO2(NO3)2- and AnIVO2(NO3)2- revealed significantly higher energies. Previous computations for bare AnO2+ indicated AnVO2+ for An = Pu, Am, Cf, and Bk, but CmIIIO2+: electron donation from nitrate ligands has here stabilized the first CmV complex, CmVO2(NO3)2-. Structural parameters and bonding analyses indicate increasing An-NO3 bond covalency from Pu to Cf, in accordance with principles for actinide separations. Atomic ionization energies effectively predict relative stabilities of oxidation states; more reliable energies are needed for the actinides.

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1631597
Journal Information:
Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 15 Vol. 57; ISSN 0020-1669
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

References (72)

Lanthanide and Actinide Chemistry book January 2006
Chemical Bonds without Bonding Electron Density ? Does the Difference Electron-Density Analysis Suffice for a Description of the Chemical Bond? journal August 1984
Pentavalent Lanthanide Compounds: Formation and Characterization of Praseodymium(V) Oxides journal April 2016
Oxidation State 10 Exists journal June 2016
On the Upper Limits of Oxidation States in Chemistry journal February 2018
Covalency in CeIV and UIV Halide and N-Heterocyclic Carbene Bonds journal July 2010
Remarkably High Stability of Late Actinide Dioxide Cations: Extending Chemistry to Pentavalent Berkelium and Californium journal November 2017
Relationship between Electron Affinity and Half-Wave Reduction Potential: A Theoretical Study on Cyclic Electron-Acceptor Compounds journal September 2016
Molcas 8: New capabilities for multiconfigurational quantum chemical calculations across the periodic table : Molcas 8 journal November 2015
Electron transfer dissociation of dipositive uranyl and plutonyl coordination complexes: ETD of Uranyl/Plutonyl Complexes journal December 2011
How to select active space for multiconfigurational quantum chemistry? journal April 2011
The Chemistry of the Actinide and Transactinide Elements book January 2006
Berkelium book January 2006
Einsteinium book January 2006
Fermium, Mendelevium, Nobelium, and Lawrencium book January 2007
Americium book January 2007
Hydration of gas-phase ytterbium ion complexes studied by experiment and theory journal February 2011
Quantum electrodynamical corrections to the fine structure of helium journal January 1974
Dirac-fock total energies, ionization energies, and orbital energies for uranium ions U I to U XCII journal November 1988
Covalency in f-element bonds journal October 2002
MOLCAS: a program package for computational chemistry journal October 2003
Recent advances in computational modeling and simulations on the An(III)/Ln(III) separation process journal July 2012
New relativistic ANO basis sets for actinide atoms journal June 2005
A DFT study of the affinity of lanthanide and actinide ions for sulfur-donor and nitrogen-donor ligands in aqueous solution journal February 2013
U–O yl Stretching Vibrations as a Quantitative Measure of the Equatorial Bond Covalency in Uranyl Complexes: A Quantum-Chemical Investigation journal November 2015
Topological Study of Bonding in Aquo and Bis(triazinyl)pyridine Complexes of Trivalent Lanthanides and Actinides: Does Covalency Imply Stability? journal August 2016
Relativistic Multireference Quantum Chemical Study of the Electronic Structure of Actinide Trioxide Molecules journal March 2017
Intermolecular interactions from a natural bond orbital, donor-acceptor viewpoint journal September 1988
Quantum Chemical Calculations and Experimental Investigations of Molecular Actinide Oxides journal January 2015
Thermodynamic Study of the Complexation of Trivalent Actinide and Lanthanide Cations by ADPTZ, a Tridentate N-Donor Ligand journal March 2005
Characterization and Comparison of Cm(III) and Eu(III) Complexed with 2,6-Di(5,6-dipropyl-1,2,4-triazin-3-yl)pyridine Using EXAFS, TRFLS, and Quantum-Chemical Methods journal November 2005
Gas-Phase Uranyl, Neptunyl, and Plutonyl: Hydration and Oxidation Studied by Experiment and Theory journal June 2012
Does Covalency Increase or Decrease across the Actinide Series? Implications for Minor Actinide Partitioning journal June 2012
Theoretical Investigation on Multiple Bonds in Terminal Actinide Nitride Complexes journal August 2014
Dissociation of Diglycolamide Complexes of Ln 3+ (Ln = La–Lu) and An 3+ (An = Pu, Am, Cm): Redox Chemistry of 4f and 5f Elements in the Gas Phase Parallels Solution Behavior journal October 2014
Experimental and Theoretical Comparison of Actinide and Lanthanide Bonding in M[N(EPR 2 ) 2 ] 3 Complexes (M = U, Pu, La, Ce; E = S, Se, Te; R = Ph, i Pr, H) journal January 2008
Density Functional Theory Investigations of the Homoleptic Tris(dithiolene) Complexes [M(dddt) 3 ] − q ( q = 3, 2 ; M = Nd 3+ and U 3+/4+ ) Related to Lanthanide(III)/Actinide(III) Differentiation journal April 2010
Second-order perturbation theory with a CASSCF reference function journal July 1990
Bonding in tris(.eta.5-cyclopentadienyl) actinide complexes. 5. A comparison of the bonding in neptunium, plutonium, and transplutonium compounds with that in lanthanide compounds and a transition-metal analog journal January 1991
Main Group Atoms and Dimers Studied with a New Relativistic ANO Basis Set December 2003
Quantum Chemistry Study of Actinide(III) and Lanthanide(III) Complexes with Tridentate Nitrogen Ligands journal August 2004
Oxidation of Gas-Phase Protactinium Ions, Pa + and Pa 2+ :  Formation and Properties of PaO 2 2+ (g), Protactinyl journal May 2006
Ionization Energies for the Actinide Mono- and Dioxides Series, from Th to Cm: Theory versus Experiment journal May 2010
Gas-Phase Energetics of Actinide Oxides: An Assessment of Neutral and Cationic Monoxides and Dioxides from Thorium to Curium † journal November 2009
Identification of an iridium-containing compound with a formal oxidation state of IX journal October 2014
The inverse-trans-influence in tetravalent lanthanide and actinide bis(carbene) complexes journal February 2017
Does covalency really increase across the 5f series? A comparison of molecular orbital, natural population, spin and electron density analyses of AnCp 3 (An = Th–Cm; Cp = η 5 -C 5 H 5 ) journal January 2011
f-Orbital covalency in the actinocenes (An = Th–Cm): multiconfigurational studies and topological analysis journal January 2014
The selectivity of diglycolamide (TODGA) and bis-triazine-bipyridine (BTBP) ligands in actinide/lanthanide complexation and solvent extraction separation – a theoretical approach journal January 2015
Synthesis and hydrolysis of gas-phase lanthanide and actinide oxide nitrate complexes: a correspondence to trivalent metal ion redox potentials and ionization energies journal January 2015
Covalency hinders AnO 2 (H 2 O) + → AnO(OH) 2 + isomerisation (An = Pa–Pu) journal January 2016
Assessing covalency in equatorial U–N bonds: density based measures of bonding in BTP and isoamethyrin complexes of uranyl journal January 2016
Ligand size dependence of U–N and U–O bond character in a series of uranyl hexaphyrin complexes: quantum chemical simulation and density based analysis journal January 2017
Emergence of comparable covalency in isostructural cerium( iv )– and uranium( iv )–carbon multiple bonds journal January 2016
Quantification of f-element covalency through analysis of the electron density: insights from simulation journal January 2017
Pentavalent lanthanide nitride-oxides: NPrO and NPrO − complexes with NPr triple bonds journal January 2017
Covalency in AnCp4 (An = Th–Cm): a comparison of molecular orbital, natural population and atoms-in-molecules analyses journal January 2010
Uncovering f-element bonding differences and electronic structure in a series of 1 : 3 and 1 : 4 complexes with a diselenophosphinate ligand journal January 2013
Oxidation state and covalency in f-element metallocenes (M = Ce, Th, Pu): a combined CASSCF and topological study journal January 2013
Valence basis sets for relativistic energy-consistent small-core actinide pseudopotentials journal January 2003
Electronic Spectra of Weak‐Field Fluoride Complexes of Tetravalent Neodymium journal November 1968
Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen journal January 1989
Second‐order perturbation theory with a complete active space self‐consistent field reference function journal January 1992
Electron affinities of the first‐row atoms revisited. Systematic basis sets and wave functions journal May 1992
Density‐functional thermochemistry. III. The role of exact exchange journal April 1993
Energy‐adjusted pseudopotentials for the actinides. Parameter sets and test calculations for thorium and thorium monoxide journal May 1994
Towards the origin of effective An(III)/Ln(III) separation by tridentate N-donor ligands: a theoretical study on atomic charges and polarisabilities for Cm(III)/Gd(III) separation journal January 2016
Relativistic electronic-structure calculations employing a two-component no-pair formalism with external-field projection operators journal June 1986
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density journal January 1988
Covalency in the actinide dioxides: Systematic study of the electronic properties using screened hybrid density functional theory journal July 2007
Oxidation-State Control of Nanoparticles Synthesized via Chemical Reduction Using Potential Diagrams journal January 2009
Assessing Covalency in Cerium and Uranium Hexachlorides: A Correlated Wavefunction and Density Functional Theory Study journal November 2015

Cited By (3)

Contemporary Chemistry of Berkelium and Californium journal June 2019
Chemical evidence of the stability of praseodymium( v ) in gas-phase oxide nitrate complexes journal January 2019
Comparison of tetravalent cerium and terbium ions in a conserved, homoleptic imidophosphorane ligand field journal January 2020

Figures / Tables (16)

Table 1(p. 10)table Table 1
Table 2(p. 11)table Table 2
Table 3(p. 12)table Table 3
Table 4(p. 14)table Table 4
Table 5(p. 17)table Table 5
Scheme 1(p. 26)figure Scheme 1
Figure 1(p. 27)figure Figure 1
Figure 2(p. 28)figure Figure 2
Figure 3(p. 29)figure Figure 3
Figure 4(p. 30)figure Figure 4
Figure 5(p. 31)figure Figure 5
Figure 6(p. 32)figure Figure 6
Figure 7(p. 33)figure Figure 7
Figure 8(p. 34)figure Figure 8
Figure 9(p. 35)figure Figure 9
Figure 10(p. 36)figure Figure 10

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:1418310
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:1596108

Related Subjects

36 MATERIALS SCIENCE