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Journal of Molecular Modeling

, Volume 17, Issue 9, pp 2259–2264 | Cite as

Crystal and electronic structures and high-pressure behavior of AgSO4, a unique narrow band gap antiferromagnetic semiconductor: LDA(+U) picture

  • Mariana DerzsiEmail author
  • Juliusz Stasiewicz
  • Wojciech Grochala
Original Paper

Abstract

We demonstrate that DFT calculations performed with the local density approximation (LDA) allow for significantly better reproduction of lattice constants, the unit cell volume and the density of Ag(II)SO4 than those done with generalized gradient approximation (GGA). The LDA+U scheme, which accounts for electronic correlation effects, enables the accurate prediction of the magnetic superexchange constant of this strongly correlated material and its band gap at the Fermi level. The character of the band gap places the compound on the borderline between a Mott insulator and a charge transfer insulator. The size of the band gap (0.82 eV) indicates that AgSO4 is a ferrimagnetic semiconductor, and possibly an attractive material for spintronics. A bulk modulus of 27.0 GPa and a compressibility of 0.037 GPa–1 were determined for AgSO4 from the third-order Birch–Murnaghan isothermal equation of state up to 20 GPa. Several polymorphic types compete with the ambient pressure P-1 phase as the external pressure is increased. The P-1 phase is predicted to resist pressure-induced metallization up to at least 20 GPa.

Figure

Despite its more simplified character, the local density approximation allows for much better reproduction of many microscopic parameters of Ag(II)SO4 than the more sophisticated generalized gradient approximation

Keywords

Density functional theory Sulfate Mixed valence Silver Solid state 

Notes

Acknowledgments

The project “Quest for Superconductivity in Crystal-Engineered Higher Fluorides of Silver” is operated by the Foundation for Polish Science’s TEAM program, and co-financed by the EU European Regional Development Fund.

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Copyright information

© Springer-Verlag 2011

Authors and Affiliations

  • Mariana Derzsi
    • 1
    Email author
  • Juliusz Stasiewicz
    • 2
  • Wojciech Grochala
    • 1
    • 2
  1. 1.ICMUniversity of WarsawWarsawPoland
  2. 2.Faculty of ChemistryUniversity of WarsawWarsawPoland

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