Lattice dynamics of pyrite FeS2 — polarizable-ion model (original) (raw)

Abstract

Lattice dynamical calculations of the pyrite FeS2 were performed using the polarizable-ion model (PIM) with different sets of short-range force constants. Not until the mean deviations between the observed and the calculated phonon energies become smaller than 3 cm-1, the true force field can be established. In the case of only slightly greater deviations, the force fields computed differ strongly being without any physical meaning. The results are discussed with respect to the force constants K i , F i , and H i , the effective dynamic charges and polarizabilities of the atoms involved, and the eigenvectors and potential energy distributions of the phonon modes. The most important short-range force constants are K 1 (Fe-S stretching): 0.5 N cm-1, K 2 (internal stretching of the S2 units): 1.0 N cm-1, F 1 (Fe....Fe stretching): 0.2 N cm-1, which indicate repulsive interactions of Fe atoms due to the occupied t 2g orbitals despite the relatively large Fe⋯Fe distances of 383 pm, and F 2 and F 3 (both intermolecular S2⋯S2 interactions): 0.2 N cm-1. The great TO/LO splittings of some of the IR allowed phonon modes (species F u) are caused by the large polarizabilities (2.4.106 and 3.3.106 pm3) of the atoms involved rather than by their effective charges (Fe: 0.2 e).

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Authors and Affiliations

1. Universität Siegen, Anorganische Chemie I, D-57068, Siegen, Germany
   H. D. Lutz & J. Zwinscher

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1. H. D. Lutz
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2. J. Zwinscher
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Dedicated to Professor Kurt Dehnicke on the occasion of his 65th birthday

This is contribution LXXXX of a series of papers on lattice vibration spectra

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Lutz, H.D., Zwinscher, J. Lattice dynamics of pyrite FeS2 — polarizable-ion model.Phys Chem Minerals 23, 497–502 (1996). https://doi.org/10.1007/BF00241999

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• Received: 16 January 1996
• Accepted: 23 June 1996
• Issue Date: December 1996
• DOI: https://doi.org/10.1007/BF00241999

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