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Title: Cluster embedding of ionic systems: Point charges and extended ions

Abstract

The embedding of cluster models of oxides with point charges and with extensions of the embedding which take into account the spatial extent of the cations is examined with an emphasis on the consequences of this embedding for the relative ionization and excitation energies that are measured in core-level spectroscopies. It is found that the dependence of the electronic structure of the oxides and the relative energies of different levels depend only weakly on the embedding and that relatively simple embeddings may be sufficient to provide an adequate model for determining core-level spectra. This is different from absolute values of the ionizations which, as expected, depend strongly on the details of the extended crystal; however, relative values of binding energies, as measured in photoemission, are of greater interest than the absolute values.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2]
  1. Univ. of North Texas, Denton, TX (United States)
  2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1605894
Report Number(s):
PNNL-SA-147745
Journal ID: ISSN 0021-9606
Grant/Contract Number:  
AC05-76RL01830
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 151; Journal Issue: 4; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Angular momentum coupling; Relativistic effects; Spin-orbit interactions; Chemical bonding; Core level spectroscopy; Excitation energies; Transition metal oxides; Ions and properties; Ligand fields

Citation Formats

Bagus, Paul S., Sassi, Michel J., and Rosso, Kevin M. Cluster embedding of ionic systems: Point charges and extended ions. United States: N. p., 2019. Web. doi:10.1063/1.5108728.
Bagus, Paul S., Sassi, Michel J., & Rosso, Kevin M. Cluster embedding of ionic systems: Point charges and extended ions. United States. doi:https://doi.org/10.1063/1.5108728
Bagus, Paul S., Sassi, Michel J., and Rosso, Kevin M. Mon . "Cluster embedding of ionic systems: Point charges and extended ions". United States. doi:https://doi.org/10.1063/1.5108728. https://www.osti.gov/servlets/purl/1605894.
@article{osti_1605894,
title = {Cluster embedding of ionic systems: Point charges and extended ions},
author = {Bagus, Paul S. and Sassi, Michel J. and Rosso, Kevin M.},
abstractNote = {The embedding of cluster models of oxides with point charges and with extensions of the embedding which take into account the spatial extent of the cations is examined with an emphasis on the consequences of this embedding for the relative ionization and excitation energies that are measured in core-level spectroscopies. It is found that the dependence of the electronic structure of the oxides and the relative energies of different levels depend only weakly on the embedding and that relatively simple embeddings may be sufficient to provide an adequate model for determining core-level spectra. This is different from absolute values of the ionizations which, as expected, depend strongly on the details of the extended crystal; however, relative values of binding energies, as measured in photoemission, are of greater interest than the absolute values.},
doi = {10.1063/1.5108728},
journal = {Journal of Chemical Physics},
number = 4,
volume = 151,
place = {United States},
year = {2019},
month = {7}
}

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Works referenced in this record:

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

Covalent bonding in heavy metal oxides
journal, April 2017

  • Bagus, Paul S.; Nelin, Connie J.; Hrovat, Dave A.
  • The Journal of Chemical Physics, Vol. 146, Issue 13
  • DOI: 10.1063/1.4979018

A b i n i t i o model potential study of local distortions around Cr + and Cr 3+ defects in fluorite
journal, June 1991

  • Seijo, Luis; Barandiarán, Zoila
  • The Journal of Chemical Physics, Vol. 94, Issue 12
  • DOI: 10.1063/1.460098

Covalent interactions in oxides
journal, June 2014


Extracting Chemical Information from XPS Spectra: A Perspective
journal, May 2018


Embedding a multideterminantal wave function in an orbital-free environment
journal, January 2008


The role of the 5f valence orbitals of early actinides in chemical bonding
journal, July 2017

  • Vitova, T.; Pidchenko, I.; Fellhauer, D.
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms16053

Ionization and excitation energies in CuCl and NiO within different embedding schemes
journal, January 1998


Analysis of X-ray adsorption edges: L 2,3 edge of FeCl 4
journal, December 2017

  • Bagus, Paul S.; Nelin, Connie J.; Ilton, Eugene S.
  • The Journal of Chemical Physics, Vol. 147, Issue 22
  • DOI: 10.1063/1.5006223

Self-consistent-field studies of core-level shifts in ionic crystals. II. MgO and BeO
journal, August 1987


Madelung fields from optimized point charges for ab initio cluster model calculations on ionic systems
journal, June 1993

  • Sousa, C.; Casanovas, J.; Rubio, J.
  • Journal of Computational Chemistry, Vol. 14, Issue 6
  • DOI: 10.1002/jcc.540140608

Ab initio absorption spectrum of NiO combining molecular dynamics with the embedded cluster approach in a discrete reaction field
journal, April 2012


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

A New Mechanism For XPS Line Broadening: The 2p-XPS of Ti(IV)
journal, July 2018

  • Bagus, Paul S.; Nelin, Connie J.; Brundle, C. R.
  • The Journal of Physical Chemistry C, Vol. 123, Issue 13
  • DOI: 10.1021/acs.jpcc.8b05576

Surface core-level binding energy shifts for MgO(100)
journal, January 2014

  • Nelin, Connie J.; Uhl, Felix; Staemmler, Volker
  • Phys. Chem. Chem. Phys., Vol. 16, Issue 40
  • DOI: 10.1039/c4cp03369h

Frozen density functional approach for ab initio calculations of solvated molecules
journal, July 1993

  • Wesolowski, Tomasz Adam; Warshel, Arieh
  • The Journal of Physical Chemistry, Vol. 97, Issue 30
  • DOI: 10.1021/j100132a040

Ab initio molecular simulations with numeric atom-centered orbitals
journal, November 2009

  • Blum, Volker; Gehrke, Ralf; Hanke, Felix
  • Computer Physics Communications, Vol. 180, Issue 11
  • DOI: 10.1016/j.cpc.2009.06.022

Multiconfigurational Self-Consistent Field Theory with Density Matrix Embedding: The Localized Active Space Self-Consistent Field Method
journal, November 2018

  • Hermes, Matthew R.; Gagliardi, Laura
  • Journal of Chemical Theory and Computation, Vol. 15, Issue 2
  • DOI: 10.1021/acs.jctc.8b01009

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


Combining Wave Function Methods with Density Functional Theory for Excited States
journal, April 2018


The effect of symmetry on the U L 3 NEXAFS of octahedral coordinated uranium( vi )
journal, March 2017

  • Bagus, Paul S.; Nelin, Connie J.; Ilton, Eugene S.
  • The Journal of Chemical Physics, Vol. 146, Issue 11
  • DOI: 10.1063/1.4978481

Quantum chemical analysis of the bond lengths in fn and fn−1d1 states of Ce3+, Pr3+, Pa4+, and U4+ defects in chloride hosts
journal, August 2003

  • Barandiarán, Zoila; Seijo, Luis
  • The Journal of Chemical Physics, Vol. 119, Issue 7
  • DOI: 10.1063/1.1590952

Calculation of local excitations in large systems by embedding wave-function theory in density-functional theory
journal, January 2008

  • Gomes, André Severo Pereira; Jacob, Christoph R.; Visscher, Lucas
  • Physical Chemistry Chemical Physics, Vol. 10, Issue 35
  • DOI: 10.1039/b805739g

General Purpose Electrostatic Embedding Potential
journal, February 2010

  • Sushko, Peter V.; Abarenkov, Igor V.
  • Journal of Chemical Theory and Computation, Vol. 6, Issue 4
  • DOI: 10.1021/ct900480p

Relativistic quantum chemistry: the MOLFDIR program package
journal, June 1994


Density functional theory with an approximate kinetic energy functional applied to study structure and stability of weak van der Waals complexes
journal, April 1998

  • Wesołowski, T. A.; Ellinger, Y.; Weber, J.
  • The Journal of Chemical Physics, Vol. 108, Issue 15
  • DOI: 10.1063/1.476018

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

Consequences of realistic embedding for the L 2,3 edge XAS of α-Fe 2 O 3
journal, January 2018

  • Bagus, Paul S.; Nelin, Connie J.; Sassi, Michel
  • Physical Chemistry Chemical Physics, Vol. 20, Issue 6
  • DOI: 10.1039/c7cp06926j

On the Stability of Certain Heteropolar Crystals
journal, February 1932


Crystal field and magnetic structure of UO 2
journal, February 2011


    Works referencing / citing this record:

    Analysis of the Fe 2p XPS for hematite α Fe 2 O 3 : Consequences of covalent bonding and orbital splittings on multiplet splittings
    journal, January 2020

    • Bagus, Paul S.; Nelin, Connie J.; Brundle, C. R.
    • The Journal of Chemical Physics, Vol. 152, Issue 1
    • DOI: 10.1063/1.5135595