Probing Actinide Electronic Structure through Pu Cluster Calculations

Ryzhkov, Mickhail V.; Mirmelstein, Alexei; Yu, Sung-Woo; Chung, Brandon W.; Tobin, James G.

doi:10.1002/qua.24417

Title: Probing Actinide Electronic Structure through Pu Cluster Calculations

Journal Article · Tue Feb 26 00:00:00 EST 2013 · International Journal of Quantum Chemistry

DOI:https://doi.org/10.1002/qua.24417· OSTI ID:1237579

Ryzhkov, Mickhail V. ^[1]; Mirmelstein, Alexei ^[2]; Yu, Sung-Woo ^[3]; Chung, Brandon W. ^[3]; Tobin, James G. ^[3]

Russian Academy of Sciences (RAS), Ekaterinburg (Russian Federation)
Russian Federal Nuclear Center, Snezhinsk (Russia)
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

The calculations for the electronic structure of clusters of plutonium have been performed, within the framework of the relativistic discrete-variational method. Moreover, these theoretical results and those calculated earlier for related systems have been compared to spectroscopic data produced in the experimental investigations of bulk systems, including photoelectron spectroscopy. Observation of the changes in the Pu electronic structure as a function of size provides powerful insight for aspects of bulk Pu electronic structure.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC52-07NA27344

OSTI ID:: 1237579

Report Number(s):: LLNL-JRNL-524554

Journal Information:: International Journal of Quantum Chemistry, Vol. 113; ISSN 0020-7608

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 11 works

Citation information provided by
Web of Science

References (47)

Possible existence of the plutonium dimer Archibong, Edet F.; Ray, Asok K. Physical Review A, Vol. 60, Issue 6 https://doi.org/10.1103/physreva.60.5105	journal	December 1999
Similarities in Magnetic Behavior of Cerium and Plutonium Compounds Cooper, Bernard R.; Thayamballi, P.; Spirlet, J. C. Physical Review Letters, Vol. 51, Issue 26 https://doi.org/10.1103/physrevlett.51.2418	journal	December 1983
Fully relativistic calculations of ThF4 Ryzhkov, M. V.; Teterin, A. Yu.; Teterin, Yu. A. International Journal of Quantum Chemistry, Vol. 110, Issue 14 https://doi.org/10.1002/qua.22406	journal	August 2010
Self-consistent embedded-cluster model for magnetic impurities: Fe, Co, and Ni in $β^{'}$ --NiAl Ellis, D. E.; Benesh, G. A.; Byrom, E. Physical Review B, Vol. 20, Issue 3 https://doi.org/10.1103/physrevb.20.1198	journal	August 1979
Direct comparison of spectroscopic data with cluster calculations of plutonium dioxide and uranium dioxide Tobin, J. G.; Yu, S. -W.; Chung, B. W. Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 31, Issue 1 https://doi.org/10.1116/1.4772959	journal	January 2013
Electronic spectroscopy and ionization potential of UO2 in the gas phase Han, Jiande; Goncharov, Vasiliy; Kaledin, Leonid A. The Journal of Chemical Physics, Vol. 120, Issue 11 https://doi.org/10.1063/1.1647531	journal	March 2004
Instrument for the investigation of the nanostructure of Pu and other actinides Trelenberg, T. W.; Glade, S. C.; Felter, T. E. Review of Scientific Instruments, Vol. 75, Issue 3 https://doi.org/10.1063/1.1647695	journal	March 2004
From molecules to solids with the DMol3 approach Delley, B. The Journal of Chemical Physics, Vol. 113, Issue 18 https://doi.org/10.1063/1.1316015	journal	November 2000
An all‐electron numerical method for solving the local density functional for polyatomic molecules Delley, B. The Journal of Chemical Physics, Vol. 92, Issue 1 https://doi.org/10.1063/1.458452	journal	January 1990
The ab initio ground state properties and magnetic structure of plutonium Kutepov, A. L.; Kutepova, S. G. Journal of Physics: Condensed Matter, Vol. 15, Issue 17 https://doi.org/10.1088/0953-8984/15/17/315	journal	April 2003
First-principles study of electronic structure and insulating properties of uranium and plutonium dioxides Ryzhkov, M. V.; Kupryazhkin, A. Ya. Journal of Nuclear Materials, Vol. 384, Issue 3 https://doi.org/10.1016/j.jnucmat.2008.11.011	journal	February 2009
Crystal orbital Hamilton populations (COHP): energy-resolved visualization of chemical bonding in solids based on density-functional calculations Dronskowski, Richard; Bloechl, Peter E. The Journal of Physical Chemistry, Vol. 97, Issue 33 https://doi.org/10.1021/j100135a014	journal	August 1993
The Electronic Spectrum of the UO ₂ Molecule Gagliardi, Laura; Heaven, Michael C.; Krogh, Jesper Wisborg Journal of the American Chemical Society, Vol. 127, Issue 1 https://doi.org/10.1021/ja044940l	journal	January 2005
Gas-Phase Energetics of Actinide Oxides: An Assessment of Neutral and Cationic Monoxides and Dioxides from Thorium to Curium ^† Marçalo, Joaquim; Gibson, John K. The Journal of Physical Chemistry A, Vol. 113, Issue 45 https://doi.org/10.1021/jp904862a	journal	November 2009
Multiconfigurational nature of 5f orbitals in uranium and plutonium intermetallics Booth, C. H.; Jiang, Y.; Wang, D. L. Proceedings of the National Academy of Sciences, Vol. 109, Issue 26 https://doi.org/10.1073/pnas.1200725109	journal	June 2012
Photoelectron spectroscopy study of the $5 f$ localization in Pu Havela, L.; Gouder, T.; Wastin, F. Physical Review B, Vol. 65, Issue 23 https://doi.org/10.1103/physrevb.65.235118	journal	June 2002
Energy calibrations in the x-ray absorption spectroscopy of uranium dioxide Yu, Sung Woo; Tobin, J. G.; Olalde-Velasco, Paul Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 30, Issue 1 https://doi.org/10.1116/1.3670402	journal	January 2012
Electronic structure of endohedral fullerenes An@C28 (An=Th – Md) Ryzhkov, Mikhail V.; Ivanovskii, Alexander L.; Delley, Bernard Computational and Theoretical Chemistry, Vol. 985 https://doi.org/10.1016/j.comptc.2012.01.037	journal	April 2012
A Predicted Organometallic Series Following a 32-Electron Principle: An@C ₂₈ (An = Th, Pa ⁺ , U ²⁺ , Pu ⁴⁺ ) Dognon, Jean-Pierre; Clavaguéra, Carine; Pyykkö, Pekka Journal of the American Chemical Society, Vol. 131, Issue 1 https://doi.org/10.1021/ja806811p	journal	January 2009
Rocky Flats closure: The role of models in facilitating scientific communication with stakeholder groups Clark, David L.; Choppin, Gregory R.; Dayton, Christine S. Journal of Alloys and Compounds, Vol. 444-445 https://doi.org/10.1016/j.jallcom.2007.02.121	journal	October 2007
Substitution of Pb by Ag as a way to obtain new high temperature superconductors: A quantum chemical point of view Ryzhkov, M. V.; Medvedeva, N. I.; Gubanov, V. A. Journal of Physics and Chemistry of Solids, Vol. 56, Issue 9 https://doi.org/10.1016/0022-3697(95)00012-7	journal	September 1995
On the Electronic Structure of Molecular UO ₂ in the Presence of Ar Atoms: Evidence for Direct U−Ar Bonding Li, Jun; Bursten, Bruce E.; Andrews, Lester Journal of the American Chemical Society, Vol. 126, Issue 11 https://doi.org/10.1021/ja039933w	journal	March 2004
Electronic properties of f -electron metals using the generalized gradient approximation Söderlind, P.; Eriksson, O.; Johansson, B. Physical Review B, Vol. 50, Issue 11 https://doi.org/10.1103/physrevb.50.7291	journal	September 1994
Particle-Size-Induced Valence Changes in Samarium Clusters Mason, M. G.; Lee, S. -T.; Apai, G. Physical Review Letters, Vol. 47, Issue 10 https://doi.org/10.1103/physrevlett.47.730	journal	September 1981
Electronic structure of the (111) and (100) surfaces of δ-Pu Hao, You Gong; Eriksson, Olle; Fernando, Gayanath W. Physical Review B, Vol. 43, Issue 12 https://doi.org/10.1103/physrevb.43.9467	journal	April 1991
Actinide Carbonte Complexes and Their Importance in Actinide Environmental Chemistry Clark, David L.; Hobart, David E.; Neu, Mary P. Chemical Reviews, Vol. 95, Issue 1 https://doi.org/10.1021/cr00033a002	journal	January 1995
An instrument for the investigation of actinides with spin resolved photoelectron spectroscopy and bremsstrahlung isochromat spectroscopy Yu, S. -W.; Tobin, J. G.; Chung, B. W. Review of Scientific Instruments, Vol. 82, Issue 9 https://doi.org/10.1063/1.3638464	journal	September 2011
Photoabsorption and photoion spectroscopy of atomic uranium in the region of $6 p$ and $5 d$ excitations van Kampen, P.; Gerth, Ch.; Martins, M. Physical Review A, Vol. 61, Issue 6 https://doi.org/10.1103/physreva.61.062706	journal	May 2000
The production and oxidation of uranium nanoparticles produced via pulsed laser ablation Trelenberg, T. W.; Glade, S. C.; Tobin, J. G. Surface Science, Vol. 600, Issue 11 https://doi.org/10.1016/j.susc.2006.03.028	journal	June 2006
Importance of full Coulomb interactions for understanding the electronic structure of $δ -Pu$ Gorelov, E.; Kolorenč, J.; Wehling, T. Physical Review B, Vol. 82, Issue 8 https://doi.org/10.1103/physrevb.82.085117	journal	August 2010
Electronic structure and chemical bonding in KTiOPO ₄ Ryzhkov, M. V.; Medvedeva, N. I.; Gubanov, V. A. Physica Scripta, Vol. 48, Issue 5 https://doi.org/10.1088/0031-8949/48/5/021	journal	November 1993
Relativistic molecular calculations in the Dirac–Slater model Rosen, A.; Ellis, D. E. The Journal of Chemical Physics, Vol. 62, Issue 8 https://doi.org/10.1063/1.430892	journal	April 1975
On the electronic configuration in Pu: spectroscopy and theory Tobin, J. G.; Söderlind, P.; Landa, A. Journal of Physics: Condensed Matter, Vol. 20, Issue 12 https://doi.org/10.1088/0953-8984/20/12/125204	journal	February 2008
Evolution of band structure in gold clusters as studied by photoemission Lee, S. -T.; Apai, G.; Mason, M. G. Physical Review B, Vol. 23, Issue 2 https://doi.org/10.1103/physrevb.23.505	journal	January 1981
Speciation and Unusual Reactivity in PuO ₂₊ _x Conradson, Steven D.; Begg, Bruce D.; Clark, David L. Inorganic Chemistry, Vol. 42, Issue 12 https://doi.org/10.1021/ic026044l	journal	June 2003
Wannier-type atomic functions and chemical bonding in crystals Smirnov, V. P.; Evarestov, R. A.; Usvyat, D. E. International Journal of Quantum Chemistry, Vol. 88, Issue 5 https://doi.org/10.1002/qua.10215	journal	May 2002
Electronic structure of supported small metal clusters Mason, M. G. Physical Review B, Vol. 27, Issue 2 https://doi.org/10.1103/PhysRevB.27.748	journal	January 1983
Ag/Cu(001): Observation of the development of the electronic structure in metal overlayers from two to three dimensionality Tobin, J. G.; Robey, S. W.; Klebanoff, L. E. Physical Review B, Vol. 28, Issue 10 https://doi.org/10.1103/PhysRevB.28.6169	journal	November 1983
Valence-band photoemission from a quantum-dot system Colvin, V. L.; Alivisatos, A. P.; Tobin, J. G. Physical Review Letters, Vol. 66, Issue 21 https://doi.org/10.1103/PhysRevLett.66.2786	journal	May 1991
Covalency in the actinide dioxides: Systematic study of the electronic properties using screened hybrid density functional theory Prodan, Ionut D.; Scuseria, Gustavo E.; Martin, Richard L. Physical Review B, Vol. 76, Issue 3 https://doi.org/10.1103/PhysRevB.76.033101	journal	July 2007
Exchange and correlation in atoms, molecules, and solids by the spin-density-functional formalism Gunnarsson, O.; Lundqvist, B. I. Physical Review B, Vol. 13, Issue 10 https://doi.org/10.1103/PhysRevB.13.4274	journal	May 1976
Electronic structure of solid uranium tetrafluoride ${UF}_{4}$ Teterin, A. Yu.; Teterin, Yu. A.; Maslakov, K. I. Physical Review B, Vol. 74, Issue 4 https://doi.org/10.1103/PhysRevB.74.045101	journal	July 2006
Orbital Specificity in the Unoccupied States of ${UO}_{2}$ from Resonant Inverse Photoelectron Spectroscopy Tobin, J. G.; Yu, S. -W. Physical Review Letters, Vol. 107, Issue 16 https://doi.org/10.1103/PhysRevLett.107.167406	journal	October 2011
$f$ - $f$ origin of the insulating state in uranium dioxide: X-ray absorption experiments and first-principles calculations Yu, S. -W.; Tobin, J. G.; Crowhurst, J. C. Physical Review B, Vol. 83, Issue 16 https://doi.org/10.1103/PhysRevB.83.165102	journal	April 2011
Atomic subshell photoionization cross sections and asymmetry parameters: 1 ⩽ Z ⩽ 103 Yeh, J. J.; Lindau, I. Atomic Data and Nuclear Data Tables, Vol. 32, Issue 1 https://doi.org/10.1016/0092-640X(85)90016-6	journal	January 1985
Valence fluctuations in thin films and the $α$ and $δ$ phases of Pu metal determined by $4 f$ core-level photoemission calculations van der Laan, G.; Taguchi, M. Physical Review B, Vol. 82, Issue 4 https://doi.org/10.1103/PhysRevB.82.045114	journal	July 2010
Multiconfigurational nature of 5f orbitals in uranium and plutonium intermetallics Booth, C. H.; Jiang, Yu; Wang, D. L. arXiv https://doi.org/10.48550/arxiv.1208.2234	text	January 2012

Cited By (2)

The Issue of Pu 5f Occupation Tobin, J. G. MRS Advances, Vol. 3, Issue 53 https://doi.org/10.1557/adv.2018.372	journal	January 2018
Observation of 5f intermediate coupling in uranium x-ray emission spectroscopy Tobin, J. G.; Nowak, S.; Yu, S-W Journal of Physics Communications, Vol. 4, Issue 1 https://doi.org/10.1088/2399-6528/ab6940	journal	January 2020

Similar Records

Comparison of Spectroscopic Data with Cluster Calculations of Plutonium, Plutonium Dioxide and Uranium Dioxide

Conference · Tue May 15 00:00:00 EDT 2012 · OSTI ID:1237579

Tobin, J G; Yu, S W; Chung, B W; +2 more

Molecular cluster theory of chemical bonding in actinide oxide. [Monoxides and dioxides]

Conference · Sun Jan 01 00:00:00 EST 1978 · OSTI ID:1237579

Ellis, D E; Gubanov, V A; Rosen, A

Probing the Electronic Structure of Early Transition-Metal Oxide Clusters: Polyhedral Cages of (V ₂ O ₅ ) _n ^- ( n = 2-4) and (M ₂ O ₅ ) ₂ ^- (M = Nb, Ta)

Journal Article · Mon Oct 01 00:00:00 EDT 2007 · Journal of the American Chemical Society · OSTI ID:1237579

Zhai, Hua-Jin; Döbler, Jens; Sauer, Joachim; +1 more

Related Subjects

75 CONDENSED MATTER PHYSICS
SUPERCONDUCTIVITY AND SUPERFLUIDITY

Title: Probing Actinide Electronic Structure through Pu Cluster Calculations

Citation Formats

References (47)

Cited By (2)

Similar Records

Related Subjects