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Title: Covalent bonding in heavy metal oxides

Abstract

Novel theoretical methods were used to quantify the magnitude and the energetic contributions of 4f/5f-O2p and 5d/6d-O2p interactions to covalent bonding in lanthanide and actinide oxides. Although many analyses have neglected the involvement of the frontier d orbitals, the present study shows that f and d covalency are of comparable importance. Two trends are identified. As is expected, the covalent mixing is larger when the nominal oxidation state is higher. More subtly, the importance of the nf covalent mixing decreases sharply relative to (n+1)d as the nf occupation increases. Atomic properties of the metal cations that drive these trends are identified.

Authors:
ORCiD logo; ; ORCiD logo;
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1372960
Report Number(s):
PNNL-SA-123570
Journal ID: ISSN 0021-9606; KC0302060
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 146; Journal Issue: 13; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English

Citation Formats

Bagus, Paul S., Nelin, Connie J., Hrovat, Dave A., and Ilton, Eugene S. Covalent bonding in heavy metal oxides. United States: N. p., 2017. Web. doi:10.1063/1.4979018.
Bagus, Paul S., Nelin, Connie J., Hrovat, Dave A., & Ilton, Eugene S. Covalent bonding in heavy metal oxides. United States. doi:10.1063/1.4979018.
Bagus, Paul S., Nelin, Connie J., Hrovat, Dave A., and Ilton, Eugene S. Fri . "Covalent bonding in heavy metal oxides". United States. doi:10.1063/1.4979018.
@article{osti_1372960,
title = {Covalent bonding in heavy metal oxides},
author = {Bagus, Paul S. and Nelin, Connie J. and Hrovat, Dave A. and Ilton, Eugene S.},
abstractNote = {Novel theoretical methods were used to quantify the magnitude and the energetic contributions of 4f/5f-O2p and 5d/6d-O2p interactions to covalent bonding in lanthanide and actinide oxides. Although many analyses have neglected the involvement of the frontier d orbitals, the present study shows that f and d covalency are of comparable importance. Two trends are identified. As is expected, the covalent mixing is larger when the nominal oxidation state is higher. More subtly, the importance of the nf covalent mixing decreases sharply relative to (n+1)d as the nf occupation increases. Atomic properties of the metal cations that drive these trends are identified.},
doi = {10.1063/1.4979018},
journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 13,
volume = 146,
place = {United States},
year = {2017},
month = {4}
}

Works referenced in this record:

The nature of the bonding of CN to metals and organic molecules
journal, August 1987

  • Nelin, C. J.; Bagus, P. S.; Philpott, M. R.
  • The Journal of Chemical Physics, Vol. 87, Issue 4
  • DOI: 10.1063/1.453142

Decomposition of the chemisorption bond by constrained variations: Order of the variations and construction of the variational spaces
journal, June 1992

  • Bagus, Paul S.; Illas, Francesc
  • The Journal of Chemical Physics, Vol. 96, Issue 12
  • DOI: 10.1063/1.462875

Natural population analysis
journal, July 1985

  • Reed, Alan E.; Weinstock, Robert B.; Weinhold, Frank
  • The Journal of Chemical Physics, Vol. 83, Issue 2
  • DOI: 10.1063/1.449486

Covalent interactions in oxides
journal, June 2014


Natural localized molecular orbitals
journal, August 1985

  • Reed, Alan E.; Weinhold, Frank
  • The Journal of Chemical Physics, Vol. 83, Issue 4
  • DOI: 10.1063/1.449360

Self-Consistent Field Theory for Open Shells of Electronic Systems
journal, April 1960


The metal–carbonyl bond in Ni(CO) 4 and Fe(CO) 5 : A clear‐cut analysis
journal, December 1984

  • Bauschlicher, Charles W.; Bagus, Paul S.
  • The Journal of Chemical Physics, Vol. 81, Issue 12
  • DOI: 10.1063/1.447589

Theoretical modeling of the uranium 4f XPS for U(VI) and U(IV) oxides
journal, December 2013

  • Bagus, Paul S.; Nelin, Connie J.; Ilton, Eugene S.
  • The Journal of Chemical Physics, Vol. 139, Issue 24
  • DOI: 10.1063/1.4846135

Theoretical analysis of the U L 3 -edge NEXAFS in U oxides
journal, January 2014

  • Nelin, Connie J.; Bagus, Paul S.; Ilton, Eugene S.
  • RSC Adv., Vol. 4, Issue 14
  • DOI: 10.1039/c3ra46738d

Defining the contributions of permanent electrostatics, Pauli repulsion, and dispersion in density functional theory calculations of intermolecular interaction energies
journal, March 2016

  • Horn, Paul R.; Mao, Yuezhi; Head-Gordon, Martin
  • The Journal of Chemical Physics, Vol. 144, Issue 11
  • DOI: 10.1063/1.4942921

Electronic Population Analysis of Molecular Wavefunctions
journal, May 1967

  • Davidson, Ernest R.
  • The Journal of Chemical Physics, Vol. 46, Issue 9
  • DOI: 10.1063/1.1841219

Frozen fragment reduced variational space analysis of hydrogen bonding interactions. Application to the water dimer
journal, August 1987


Spin–orbit coupling in actinide cations
journal, September 2012


Effective core potential methods for the lanthanides
journal, April 1993

  • Cundari, Thomas R.; Stevens, Walter J.
  • The Journal of Chemical Physics, Vol. 98, Issue 7
  • DOI: 10.1063/1.464902

Covalency in f-element complexes
journal, January 2013

  • Neidig, Michael L.; Clark, David L.; Martin, Richard L.
  • Coordination Chemistry Reviews, Vol. 257, Issue 2
  • DOI: 10.1016/j.ccr.2012.04.029

The interpretation of XPS spectra: Insights into materials properties
journal, June 2013


Titration of Ce 3 + Ions in the CeO 2 ( 111 ) Surface by Au Adatoms
journal, November 2013


Alternative definitions of the frozen energy in energy decomposition analysis of density functional theory calculations
journal, February 2016

  • Horn, Paul R.; Head-Gordon, Martin
  • The Journal of Chemical Physics, Vol. 144, Issue 8
  • DOI: 10.1063/1.4941849

A crystal field calculation in uranium dioxide
journal, November 1966


A new analysis of charge transfer and polarization for ligand–metal bonding: Model studies of Al 4 CO and Al 4 NH 3
journal, May 1984

  • Bagus, Paul S.; Hermann, K.; Bauschlicher, Charles W.
  • The Journal of Chemical Physics, Vol. 80, Issue 9
  • DOI: 10.1063/1.447215

Charge transfer satellites and multiplet splitting in X-ray photoemission spectra of late transition metal halides
journal, June 1992

  • Okada, K.; Kotani, A.; Thole, B. T.
  • Journal of Electron Spectroscopy and Related Phenomena, Vol. 58, Issue 4
  • DOI: 10.1016/0368-2048(92)85018-3

Electronic Population Analysis on LCAO–MO Molecular Wave Functions. I
journal, October 1955

  • Mulliken, R. S.
  • The Journal of Chemical Physics, Vol. 23, Issue 10
  • DOI: 10.1063/1.1740588