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The Performance of Hybrid Density Functionals in Solid State Chemistry

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Principles and Applications of Density Functional Theory in Inorganic Chemistry II

Part of the book series: Structure and Bonding ((STRUCTURE,volume 113))

Abstract

We examine the performance of hybrid (HF-DFT) exchange functionals within Density Functional Theory (DFT) in describing the properties of crystalline solids. Recent applications are reviewed, and an extensive set of new results presented on transition metal compounds.

The features of the electronic density and of several calculated properties are examined as the weight of the HF (exact) exchange in the hybrid functional is increased. Clear trends emerge in the structural and electronic properties; in particular, HF exchange increases the electronic localisation. This features causes an increase in the ionicity of the materials, a systematic decrease of the lattice parameter and increase of the elastic constants and bulk moduli. When HF and standard (LDA or GGA) DFT solutions yield systematically results with opposite sign with respect to experiment, the formulation of hybrid functionals improves the accuracy of the calculations. This is the case for band gaps, phonon spectra, magnetic coupling constants, and all properties that depend on the extent of electronic localisation at either perfect or defective lattice sites. A different weight of HF exchange is required to reproduce the experimental value of different observables; as a general rule, however, a higher fraction of HF exchange than the 20% optimised in the molecular B3LYP formulation is required in the solid state.

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Acknowledgements

We would like to thank the CRYSTAL group, in both Torino and Daresbury, for valuable discussions throughout the years; in particular we thank Carla Roetti, Vic Saunders and Nic Harrison; we would also like to thank Mike Finnis and Tony Paxton for making available their Tight-Binding code. FC acknowledges EPSRC for an advanced research fellowship.

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Authors and Affiliations

  1. Davy-Faraday Research Laboratory, The Royal Institution of Great Britain, 21 Albemarle Street, London, W1S 4BS, UK

    Furio Corà, Maria Alfredsson & Giuseppe Mallia

  2. School of Chemistry, University of St. Andrews, St. Andrews, Fife, KY16 9ST, UK

    Derek S. Middlemiss & William C. Mackrodt

  3. Dipartimento di Chimica IFM, Università di Torino, Via Giuria 5, 10125, Torino, Italy

    Roberto Dovesi & Roberto Orlando

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  1. Furio Corà
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  2. Maria Alfredsson
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  3. Giuseppe Mallia
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  7. Roberto Orlando
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Correspondence to Furio Corà .

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Corà, F. et al. (2004). The Performance of Hybrid Density Functionals in Solid State Chemistry. In: Principles and Applications of Density Functional Theory in Inorganic Chemistry II. Structure and Bonding, vol 113. Springer, Berlin, Heidelberg. https://doi.org/10.1007/b97944

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