Phonon Spectroscopy in Antimony and Tellurium Oxides
Abstract
α-Sb2O3 (senarmontite), β-Sb2O3 (valentinite), and α-TeO2 (paratellurite) are compounds with pronounced stereochemically active Sb and Te lone pairs. The vibrational and lattice properties of each have been previously studied but often lead to incomplete or unreliable results due to modes being inactive in infrared or Raman spectroscopy. Here in this paper, we present a study of the relationship between bonding and lattice dynamics of these compounds. Mössbauer spectroscopy is used to study the structure of Sb in α-Sb2O3 and β-Sb2O3, whereas the vibrational modes of Sb and Te for each oxide are investigated using nuclear inelastic scattering, and further information on O vibrational modes is obtained using inelastic neutron scattering. Additionally, vibrational frequencies obtained by density functional theory (DFT) calculations are compared with experimental results in order to assess the validity of the utilized functional. Good agreement was found between DFT-calculated and experimental density of phonon states with a 7% scaling factor. The Sb–O–Sb wagging mode of α-Sb2O3 whose frequency was not clear in most previous studies is experimentally observed for the first time at ~340 cm-1. Softer lattice vibrational modes occur in orthorhombic β-Sb2O3 compared to cubic α-Sb2O3, indicating that the antimony bonds are weakened upon transforming from themore »
- Authors:
-
[1];
[2];
[4];
[5];
[6];
[8];
[9];
[4];
[4];
[4];
[10]
- Forschungszentrum Julich GmbH, Julich (Germany). Julich Centre for Neutron Science (JCNS) and Peter Grunberg Inst. PGI, JARA-FIT; European Synchrotron Radiation Facility (ESRF), Grenoble (France); Univ. of Liege, (Belgium). Faculty of Sciences
- Univ. of Applied Sciences Bremerhaven, Bremerhaven (Germany). Bremerhaven Inst. of Nanotechnology
- Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- RWTH Aachen Univ. (Germany). Inst. of Inorganic Chemistry; Shenzhen Polytechnic, Shenzhen (China). Hoffmann Inst. of Advanced Materials
- RWTH Aachen Univ. (Germany). Inst. of Inorganic Chemistry; Univ. of Oxford (United Kingdom)
- RWTH Aachen Univ. (Germany). Inst. of Inorganic Chemistry
- European Synchrotron Radiation Facility (ESRF), Grenoble (France)
- Forschungszentrum Julich GmbH, Julich (Germany). Julich Centre for Neutron Science (JCNS) and Peter Grunberg Inst. PGI, JARA-FIT; Univ. of Liege, (Belgium). Faculty of Sciences
- Forschungszentrum Julich GmbH, Julich (Germany). Julich Centre for Neutron Science (JCNS) and Peter Grunberg Inst. PGI, JARA-FIT; Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Publication Date:
- Research Org.:
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1694389
- Grant/Contract Number:
- AC05-00OR22725
- Resource Type:
- Accepted Manuscript
- Journal Name:
- The Journal of Physical Chemistry A (Online)
- Additional Journal Information:
- Journal Name: The Journal of Physical Chemistry A (Online); Journal Volume: 124; Journal Issue: 39; Journal ID: ISSN 1520-5215
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Jafari, Atefeh, Klobes, Benedikt, Sergueev, Ilya, Moseley, Duncan H., Manley, Michael E., Dronskowski, Richard, Deringer, Volker L., Stoffel, Ralf P., Bessas, Dimitrios, Chumakov, Aleksandr I., Rüffer, Rudolf, Mahmoud, Abdelfattah, Bridges, Craig A., Daemen, Luke L., Cheng, Yongqiang, Ramirez-Cuesta, Anibal J., and Hermann, Raphael P. Phonon Spectroscopy in Antimony and Tellurium Oxides. United States: N. p., 2020.
Web. doi:10.1021/acs.jpca.0c05060.
Jafari, Atefeh, Klobes, Benedikt, Sergueev, Ilya, Moseley, Duncan H., Manley, Michael E., Dronskowski, Richard, Deringer, Volker L., Stoffel, Ralf P., Bessas, Dimitrios, Chumakov, Aleksandr I., Rüffer, Rudolf, Mahmoud, Abdelfattah, Bridges, Craig A., Daemen, Luke L., Cheng, Yongqiang, Ramirez-Cuesta, Anibal J., & Hermann, Raphael P. Phonon Spectroscopy in Antimony and Tellurium Oxides. United States. https://doi.org/10.1021/acs.jpca.0c05060
Jafari, Atefeh, Klobes, Benedikt, Sergueev, Ilya, Moseley, Duncan H., Manley, Michael E., Dronskowski, Richard, Deringer, Volker L., Stoffel, Ralf P., Bessas, Dimitrios, Chumakov, Aleksandr I., Rüffer, Rudolf, Mahmoud, Abdelfattah, Bridges, Craig A., Daemen, Luke L., Cheng, Yongqiang, Ramirez-Cuesta, Anibal J., and Hermann, Raphael P. Mon .
"Phonon Spectroscopy in Antimony and Tellurium Oxides". United States. https://doi.org/10.1021/acs.jpca.0c05060. https://www.osti.gov/servlets/purl/1694389.
@article{osti_1694389,
title = {Phonon Spectroscopy in Antimony and Tellurium Oxides},
author = {Jafari, Atefeh and Klobes, Benedikt and Sergueev, Ilya and Moseley, Duncan H. and Manley, Michael E. and Dronskowski, Richard and Deringer, Volker L. and Stoffel, Ralf P. and Bessas, Dimitrios and Chumakov, Aleksandr I. and Rüffer, Rudolf and Mahmoud, Abdelfattah and Bridges, Craig A. and Daemen, Luke L. and Cheng, Yongqiang and Ramirez-Cuesta, Anibal J. and Hermann, Raphael P.},
abstractNote = {α-Sb2O3 (senarmontite), β-Sb2O3 (valentinite), and α-TeO2 (paratellurite) are compounds with pronounced stereochemically active Sb and Te lone pairs. The vibrational and lattice properties of each have been previously studied but often lead to incomplete or unreliable results due to modes being inactive in infrared or Raman spectroscopy. Here in this paper, we present a study of the relationship between bonding and lattice dynamics of these compounds. Mössbauer spectroscopy is used to study the structure of Sb in α-Sb2O3 and β-Sb2O3, whereas the vibrational modes of Sb and Te for each oxide are investigated using nuclear inelastic scattering, and further information on O vibrational modes is obtained using inelastic neutron scattering. Additionally, vibrational frequencies obtained by density functional theory (DFT) calculations are compared with experimental results in order to assess the validity of the utilized functional. Good agreement was found between DFT-calculated and experimental density of phonon states with a 7% scaling factor. The Sb–O–Sb wagging mode of α-Sb2O3 whose frequency was not clear in most previous studies is experimentally observed for the first time at ~340 cm-1. Softer lattice vibrational modes occur in orthorhombic β-Sb2O3 compared to cubic α-Sb2O3, indicating that the antimony bonds are weakened upon transforming from the molecular α phase to the layer-chained β structure. The resulting vibrational entropy increase of 0.45 ± 0.1 kB/Sb2O3 at 880 K accounts for about half of the α–β transition entropy. The comparison of experimental and theoretical approaches presented here provides a detailed picture of the lattice dynamics in these oxides beyond the zone center and shows that the accuracy of DFT is sufficient for future calculations of similar material structures.},
doi = {10.1021/acs.jpca.0c05060},
journal = {The Journal of Physical Chemistry A (Online)},
number = 39,
volume = 124,
place = {United States},
year = {Mon Sep 07 00:00:00 EDT 2020},
month = {Mon Sep 07 00:00:00 EDT 2020}
}
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