DOI: 10.1063/1.467042. Charge separation and covalent bonding in metal oxide surfaces: A local density functional study on the MgO(001) surface

Charge separation and covalent bonding in metal oxide surfaces: A local density functional study on the MgO(001) surface

10.1063/1.467042

Crossref journal-article

AIP Publishing

The Journal of Chemical Physics (317)

Abstract

A first principles local density functional investigation on extended, two-dimensional periodic slab models of the MgO(001) surface is performed, using the linear combination of Gaussian-type orbitals (LCGTO) technique as implemented in the FILMS program package. Stimulated by recent theoretical evidence for a reduced charge separation in MgO(001), a detailed analysis of the charge distribution and its influence on the electrical field above the surface is carried out. Two different methods to quantify the charge separation in the ionic substrate are employed, a local one based on the topological atom approach and a global one derived from the Madelung field of the surface near potential adsorbates. Both procedures lead to a charge separation significantly (10%–20%) below the nominal ionic value of ±2 a.u. A variational atomic orbital analysis is utilized to discuss the origin of the Mg 3s and 3p structures discernible in the crystal orbitals of the MgO slab systems. They are identified as covalent magnesium valence orbital admixtures to the oxygen dominated valence bands in consistence with the reduced charge separation. Their influence on the cohesive energy of crystalline MgO, however, is found to be only 5% (∼0.5 eV).

Bibliography

Birkenheuer, U., Boettger, J. C., & RÃ¶sch, N. (1994). Charge separation and covalent bonding in metal oxide surfaces: A local density functional study on the MgO(001) surface. The Journal of Chemical Physics, 100(9), 6826â6836.

Authors 3

U. Birkenheuer (first)
J. C. Boettger (additional)
N. Rösch (additional)

References 54 Referenced 79

10.1080/01614948808078620 / Catal. Rev. Sci. Eng. (1988)
{'key': '2024020613511987800_r2'}
10.1021/cr00091a006 / Chem. Rev. (1989)
10.1016/0167-5729(92)90013-2 / Surf. Sci. Rep. (1992)
{'key': '2024020613511987800_r5'}
{'key': '2024020613511987800_r6'}
10.1103/PhysRevB.33.1308 / Phys. Rev. B (1986)
10.1016/0039-6028(86)90012-9 / Surf. Sci. (1986)
10.1088/0022-3719/20/30/020 / J. Phys. C (1987)
10.1016/S0039-6028(87)80048-1 / Surf. Sci. (1987)
10.1016/0039-6028(89)90390-7 / Surf. Sci. (1989)
10.1016/0039-6028(90)90133-S / Surf. Sci. (1990)
10.1063/1.462641 / J. Chem. Phys. (1992)
10.1002/qua.560420504 / Int. J. Quantum Chem. (1992)
{'key': '2024020613511987800_r15'}
10.1016/0301-0104(92)87161-2 / Chem. Phys. (1992)
10.1016/0039-6028(93)90266-M / Surf. Sci. (1993)
{'key': '2024020613511987800_r18'}
10.1103/PhysRevB.48.11573 / Phys. Rev. B (1993)
10.1039/ft9928800291 / J. Chem. Soc. Faraday Trans. (1992)
10.1021/j100333a005 / J. Phys. Chem. (1988)
10.1007/BF01292841 / Z. Phys. B (1981)
{'key': '2024020613511987800_r23', 'first-page': '2421', 'volume': '10', 'year': '1969', 'journal-title': 'Sov. Phys. Solid State'} / Sov. Phys. Solid State (1969)
10.1088/0022-3719/3/5/017 / J. Phys. C (1970)
10.1107/S0567739469001562 / Acta Crystallogr. Sect. A (1969)
10.1107/S0567739478001254 / Acta Crystallogr. Sect. A (1978)
10.1107/S0567739480001908 / Acta Crystallogr. Sect. A (1980)
{'key': '2024020613511987800_r28'}
10.1107/S0108768186098270 / Acta Crystallogr. Sect. B (1986)
10.1016/0039-6028(84)90549-1 / Surf. Sci. (1984)
10.1103/PhysRevB.30.4774 / Phys. Rev. B (1984)
10.1002/bbpc.19920961106 / Ber. Bunsenges. Phys. Chem. (1992)
10.1103/PhysRevB.26.1743 / Phys. Rev. B (1982)
10.1103/PhysRevB.45.1363 / Phys. Rev. B (1992)
10.1016/S0065-3276(08)60326-3 / Adv. Quantum Chem. (1981)
10.1063/1.447215 / J. Chem. Phys. (1984)
10.1088/0022-3719/15/27/024 / J. Phys. C (1982)
10.1016/0039-6028(83)90314-X / Surf. Sci. (1983)
{'key': '2024020613511987800_r39'}
{'key': '2024020613511987800_r40'}
10.1063/1.438728 / J. Chem. Phys. (1979)
10.1016/0038-1098(71)90313-9 / Solid State Commun. (1971)
10.1080/00268979100100201 / Mol. Phys. (1991)
10.1016/0167-5729(87)90007-0 / Surf. Sci. Rep. (1987)
10.1016/0009-2614(92)86008-6 / Chem. Phys. Lett. (1992)
10.1063/1.464835 / J. Chem. Phys. (1993)
{'key': '2024020613511987800_r47'}
10.1080/00268977000101561 / Mol. Phys. (1970)
10.1007/BF00767207 / Catal. Lett. (1992)
{'key': '2024020613511987800_r50'}
{'key': '2024020613511987800_r51'}
{'key': '2024020613511987800_r52'}
10.1016/S0081-1947(08)60515-9 / Solid State Phys. (1964)
10.1016/0039-6028(90)90802-F / Surf. Sci. (1990)

Dates

Type	When
Created	23 years ago (July 26, 2002, 8:12 a.m.)
Deposited	1 year, 6 months ago (Feb. 6, 2024, 9:21 a.m.)
Indexed	4 months, 1 week ago (April 11, 2025, 7:48 a.m.)
Issued	31 years, 3 months ago (May 1, 1994)
Published	31 years, 3 months ago (May 1, 1994)
Published Print	31 years, 3 months ago (May 1, 1994)

Funders 0

None

BibTeX

@article{Birkenheuer_1994, title={Charge separation and covalent bonding in metal oxide surfaces: A local density functional study on the MgO(001) surface}, volume={100}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.467042}, DOI={10.1063/1.467042}, number={9}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Birkenheuer, U. and Boettger, J. C. and Rösch, N.}, year={1994}, month=may, pages={6826–6836} }

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      "first-page": "1363",
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  "resource": {
    "primary": {
      "URL": "https://pubs.aip.org/jcp/article/100/9/6826/164658/Charge-separation-and-covalent-bonding-in-metal"
    }
  },
  "subtitle": [],
  "short-title": [],
  "issued": {
    "date-parts": [
      [
        1994,
        5,
        1
      ]
    ]
  },
  "references-count": 54,
  "journal-issue": {
    "issue": "9",
    "published-print": {
      "date-parts": [
        [
          1994,
          5,
          1
        ]
      ]
    }
  },
  "URL": "http://dx.doi.org/10.1063/1.467042",
  "relation": {},
  "ISSN": [
    "0021-9606",
    "1089-7690"
  ],
  "subject": [],
  "published-other": {
    "date-parts": [
      [
        1994,
        5,
        1
      ]
    ]
  },
  "published": {
    "date-parts": [
      [
        1994,
        5,
        1
      ]
    ]
  }
}