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Title: Structure, bonding and physical properties of tetragonal and orthorhombic SiS{sub 2} from (hybrid) DFT calculations

Abstract

The energetics, structure and physical properties of tetragonal and orthorhombic SiS{sub 2} were calculated by periodic density functional theory (DFT) calculations, using both localized orbital and projected augmented wave basis-sets. All methods applied agree upon the relative energies of the different polymorphs but show differences in the predicted geometries, which are minimized upon improving the basis-set quality. The hybrid PBE0 functional was found to give the best match between experimental and calculated structures. When comparing SiS{sub 2} with its much better studied oxide analog silica, we observe that upon substituting sulphur for oxygen, the energy landscape changes dramatically. Other effects of changing S for O are found to be smaller Si-X-Si angles, a broader distribution of X-Si-X angles, a more flexible framework and a significantly reduced band gap. The latter is in line with the experimental observation of photoluminescence in related GaGeS{sub 2} compounds and suggests that SiS{sub 2} might find application in UV light emitting diodes. Finally, a comparison of the maximally localized Wannier functions demonstrates that the Si-S bonds in SiS{sub 2} have a considerably more covalent character than the Si-O bonds in silica. - Graphical abstract: Periodic DFT calculations were employed to study the (physical) properties ofmore » tetragonal and orthorhombic SiS{sub 2}. The results obtained were compared with those for SiS{sub 2} better studied oxide analog silica and demonstrate large changes in the materials' energy landscape, nature of bonding, flexibility and band gap, upon substitution of sulphur for oxygen.« less

Authors:
 [1];  [1]
  1. Christopher Ingold Laboratories, Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ (United Kingdom)
Publication Date:
OSTI Identifier:
21128473
Resource Type:
Journal Article
Journal Name:
Journal of Solid State Chemistry
Additional Journal Information:
Journal Volume: 181; Journal Issue: 9; Other Information: DOI: 10.1016/j.jssc.2008.06.006; PII: S0022-4596(08)00295-8; Copyright (c) 2008 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0022-4596
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CHEMICAL BONDS; DENSITY FUNCTIONAL METHOD; FLEXIBILITY; ORTHORHOMBIC LATTICES; OXIDES; PHOTOLUMINESCENCE; PHYSICAL PROPERTIES; SILICA; SILICON SULFIDES; SULFUR

Citation Formats

Zwijnenburg, Martijn A., Bell, Robert G, Davy Faraday Research Laboratory, University College London, Gower Street, Kathleen Lonsdale Building, 3rd Floor, London WC1E 6BT, Cora, Furio, Davy Faraday Research Laboratory, University College London, Gower Street, Kathleen Lonsdale Building, 3rd Floor, London WC1E 6BT, and Materials Simulation Laboratory, University College London, Gower Street, London WC1E 6BT. Structure, bonding and physical properties of tetragonal and orthorhombic SiS{sub 2} from (hybrid) DFT calculations. United States: N. p., 2008. Web. doi:10.1016/j.jssc.2008.06.006.
Zwijnenburg, Martijn A., Bell, Robert G, Davy Faraday Research Laboratory, University College London, Gower Street, Kathleen Lonsdale Building, 3rd Floor, London WC1E 6BT, Cora, Furio, Davy Faraday Research Laboratory, University College London, Gower Street, Kathleen Lonsdale Building, 3rd Floor, London WC1E 6BT, & Materials Simulation Laboratory, University College London, Gower Street, London WC1E 6BT. Structure, bonding and physical properties of tetragonal and orthorhombic SiS{sub 2} from (hybrid) DFT calculations. United States. https://doi.org/10.1016/j.jssc.2008.06.006
Zwijnenburg, Martijn A., Bell, Robert G, Davy Faraday Research Laboratory, University College London, Gower Street, Kathleen Lonsdale Building, 3rd Floor, London WC1E 6BT, Cora, Furio, Davy Faraday Research Laboratory, University College London, Gower Street, Kathleen Lonsdale Building, 3rd Floor, London WC1E 6BT, and Materials Simulation Laboratory, University College London, Gower Street, London WC1E 6BT. 2008. "Structure, bonding and physical properties of tetragonal and orthorhombic SiS{sub 2} from (hybrid) DFT calculations". United States. https://doi.org/10.1016/j.jssc.2008.06.006.
@article{osti_21128473,
title = {Structure, bonding and physical properties of tetragonal and orthorhombic SiS{sub 2} from (hybrid) DFT calculations},
author = {Zwijnenburg, Martijn A. and Bell, Robert G and Davy Faraday Research Laboratory, University College London, Gower Street, Kathleen Lonsdale Building, 3rd Floor, London WC1E 6BT and Cora, Furio and Davy Faraday Research Laboratory, University College London, Gower Street, Kathleen Lonsdale Building, 3rd Floor, London WC1E 6BT and Materials Simulation Laboratory, University College London, Gower Street, London WC1E 6BT},
abstractNote = {The energetics, structure and physical properties of tetragonal and orthorhombic SiS{sub 2} were calculated by periodic density functional theory (DFT) calculations, using both localized orbital and projected augmented wave basis-sets. All methods applied agree upon the relative energies of the different polymorphs but show differences in the predicted geometries, which are minimized upon improving the basis-set quality. The hybrid PBE0 functional was found to give the best match between experimental and calculated structures. When comparing SiS{sub 2} with its much better studied oxide analog silica, we observe that upon substituting sulphur for oxygen, the energy landscape changes dramatically. Other effects of changing S for O are found to be smaller Si-X-Si angles, a broader distribution of X-Si-X angles, a more flexible framework and a significantly reduced band gap. The latter is in line with the experimental observation of photoluminescence in related GaGeS{sub 2} compounds and suggests that SiS{sub 2} might find application in UV light emitting diodes. Finally, a comparison of the maximally localized Wannier functions demonstrates that the Si-S bonds in SiS{sub 2} have a considerably more covalent character than the Si-O bonds in silica. - Graphical abstract: Periodic DFT calculations were employed to study the (physical) properties of tetragonal and orthorhombic SiS{sub 2}. The results obtained were compared with those for SiS{sub 2} better studied oxide analog silica and demonstrate large changes in the materials' energy landscape, nature of bonding, flexibility and band gap, upon substitution of sulphur for oxygen.},
doi = {10.1016/j.jssc.2008.06.006},
url = {https://www.osti.gov/biblio/21128473}, journal = {Journal of Solid State Chemistry},
issn = {0022-4596},
number = 9,
volume = 181,
place = {United States},
year = {Mon Sep 15 00:00:00 EDT 2008},
month = {Mon Sep 15 00:00:00 EDT 2008}
}