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Investigation of the chemical bonding in nickel mixed oxides from electronic structure calculations

Choisnet, J. ; Evarestov, R. A. ; Tupitsyn, I. I. and Veryazov, V. A. LU orcid (1996) In Journal of Physics and Chemistry of Solids 57(12). p.1839-1850
Abstract

The chemical bonding in a series of nickel mixed oxides, namely Li2NiO2, Na2NiO2, tetragonal and orthorhombic La2NiO4 for Ni(II), LiNiO2, NaNiO2, LaNiO3 for Ni(III), BaNiO3 for Ni(IV) and LaNiO2, 'LaSrNiO3' for Ni(I), is investigated from the results of electronic structure calculations, including both band structure and local properties, i.e. atomic charges, covalent bond orders and atomic valences. The metallic contribution to the chemical bonding is modelled on the basis of the calculation of the delocalization degree of the covalent bond order, in terms of the existence of long range M-M interactions.... (More)

The chemical bonding in a series of nickel mixed oxides, namely Li2NiO2, Na2NiO2, tetragonal and orthorhombic La2NiO4 for Ni(II), LiNiO2, NaNiO2, LaNiO3 for Ni(III), BaNiO3 for Ni(IV) and LaNiO2, 'LaSrNiO3' for Ni(I), is investigated from the results of electronic structure calculations, including both band structure and local properties, i.e. atomic charges, covalent bond orders and atomic valences. The metallic contribution to the chemical bonding is modelled on the basis of the calculation of the delocalization degree of the covalent bond order, in terms of the existence of long range M-M interactions. As a main result, the increase of the formal oxidation state of nickel in these oxides involves an increase of both its atomic charge and its covalency. The highest covalency is found for the (III) and (IV) oxidation states, as the strongest ionicity is typical of Ni(I). A special emphasis is devoted to the chemical bonding in the perovskite like nickelates. In LaNiO3, the metallicity is a 3D property, as in LaNiO2 it is a 2D one. Comparing the chemical bonding in La2NiO4 and LaSrNiO3 shows evidence for a decrease of the anisotropy of the perovskite-rocksalt intergrowth in the reduced nickelate.

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publishing date
type
Contribution to journal
publication status
published
subject
keywords
A. oxides, D. crystal structure, D. electronic structure
in
Journal of Physics and Chemistry of Solids
volume
57
issue
12
pages
12 pages
publisher
Elsevier
external identifiers
  • scopus:0030387072
ISSN
0022-3697
DOI
10.1016/S0022-3697(96)00074-1
language
English
LU publication?
no
id
0a8c7dcd-1629-4144-957e-92920114a5eb
date added to LUP
2019-05-22 14:32:34
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2022-05-03 21:14:37
@article{0a8c7dcd-1629-4144-957e-92920114a5eb,
  abstract     = {{<p>The chemical bonding in a series of nickel mixed oxides, namely Li<sub>2</sub>NiO<sub>2</sub>, Na<sub>2</sub>NiO<sub>2</sub>, tetragonal and orthorhombic La<sub>2</sub>NiO<sub>4</sub> for Ni(II), LiNiO<sub>2</sub>, NaNiO<sub>2</sub>, LaNiO<sub>3</sub> for Ni(III), BaNiO<sub>3</sub> for Ni(IV) and LaNiO<sub>2</sub>, 'LaSrNiO<sub>3</sub>' for Ni(I), is investigated from the results of electronic structure calculations, including both band structure and local properties, i.e. atomic charges, covalent bond orders and atomic valences. The metallic contribution to the chemical bonding is modelled on the basis of the calculation of the delocalization degree of the covalent bond order, in terms of the existence of long range M-M interactions. As a main result, the increase of the formal oxidation state of nickel in these oxides involves an increase of both its atomic charge and its covalency. The highest covalency is found for the (III) and (IV) oxidation states, as the strongest ionicity is typical of Ni(I). A special emphasis is devoted to the chemical bonding in the perovskite like nickelates. In LaNiO<sub>3</sub>, the metallicity is a 3D property, as in LaNiO<sub>2</sub> it is a 2D one. Comparing the chemical bonding in La<sub>2</sub>NiO<sub>4</sub> and LaSrNiO<sub>3</sub> shows evidence for a decrease of the anisotropy of the perovskite-rocksalt intergrowth in the reduced nickelate.</p>}},
  author       = {{Choisnet, J. and Evarestov, R. A. and Tupitsyn, I. I. and Veryazov, V. A.}},
  issn         = {{0022-3697}},
  keywords     = {{A. oxides; D. crystal structure; D. electronic structure}},
  language     = {{eng}},
  month        = {{12}},
  number       = {{12}},
  pages        = {{1839--1850}},
  publisher    = {{Elsevier}},
  series       = {{Journal of Physics and Chemistry of Solids}},
  title        = {{Investigation of the chemical bonding in nickel mixed oxides from electronic structure calculations}},
  url          = {{http://dx.doi.org/10.1016/S0022-3697(96)00074-1}},
  doi          = {{10.1016/S0022-3697(96)00074-1}},
  volume       = {{57}},
  year         = {{1996}},
}