The performance of hybrid density functionals in solid state chemistry

Cora, Furio and Alfredsson, Maria and Mallia, G. and Middlemiss, D.S. and Mackrodt, W.C. and Dovesi, R. and Orlando, R. (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, 113 . Springer Berlin / Heidelberg, Berlin, pp. 171-232. ISBN 978-3-540-21861-6. (The full text of this publication is not currently available from this repository. You may be able to access a copy if URLs are provided)

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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 errors 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.

Item Type: Book section
Additional information: ISI Document Delivery No.: BBK95 Times Cited: 44 Cited Reference Count: 145 Review HEIDELBERGER PLATZ 3, D-14197 BERLIN, GERMANY
Uncontrolled keywords: DFT; hybrid functionals; crystalline solids; transition metal oxides; B3LYP
Subjects: Q Science
Divisions: Faculties > Science Technology and Medical Studies > School of Physical Sciences > Functional Materials Group
Depositing User: Maria Alfredsson
Date Deposited: 08 Sep 2008 14:36
Last Modified: 07 May 2014 15:30
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