Structural and Lattice-Dynamical Properties of Tb2O3 under Compression: A Comparative Study with Rare Earth and Related Sesquioxides

We report a joint experimental and theoretical investigation of the high pressure structural and vibrational properties of terbium sesquioxide (Tb2O3). Powder X-ray diffraction and Raman scattering measurements show that cubic Ia3̅ (C-type) Tb2O3 undergoes two phase transitions up to 25 GPa. We obse...

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Autores: Ibáñez Insa, Jordi, Sans, Juan Ángel, Cuenca-Gotor, V. P., Oliva, Robert, Gomis, Óscar, Rodríguez-Hernández, P., Muñoz-Martín, Alfonso, Rodríguez-Mendoza, Ulises R., Velázquez, M., Veber, P., Popescu, Catalina, Manjón, F. J.
Tipo de recurso: artículo
Fecha de publicación:2020
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/218252
Acceso en línea:http://hdl.handle.net/10261/218252
Access Level:acceso abierto
Palabra clave:Transition Pressure
Neodymium Oxide
Sesquioxides
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dc.title.none.fl_str_mv Structural and Lattice-Dynamical Properties of Tb2O3 under Compression: A Comparative Study with Rare Earth and Related Sesquioxides
title Structural and Lattice-Dynamical Properties of Tb2O3 under Compression: A Comparative Study with Rare Earth and Related Sesquioxides
spellingShingle Structural and Lattice-Dynamical Properties of Tb2O3 under Compression: A Comparative Study with Rare Earth and Related Sesquioxides
Ibáñez Insa, Jordi
Transition Pressure
Neodymium Oxide
Sesquioxides
title_short Structural and Lattice-Dynamical Properties of Tb2O3 under Compression: A Comparative Study with Rare Earth and Related Sesquioxides
title_full Structural and Lattice-Dynamical Properties of Tb2O3 under Compression: A Comparative Study with Rare Earth and Related Sesquioxides
title_fullStr Structural and Lattice-Dynamical Properties of Tb2O3 under Compression: A Comparative Study with Rare Earth and Related Sesquioxides
title_full_unstemmed Structural and Lattice-Dynamical Properties of Tb2O3 under Compression: A Comparative Study with Rare Earth and Related Sesquioxides
title_sort Structural and Lattice-Dynamical Properties of Tb2O3 under Compression: A Comparative Study with Rare Earth and Related Sesquioxides
dc.creator.none.fl_str_mv Ibáñez Insa, Jordi
Sans, Juan Ángel
Cuenca-Gotor, V. P.
Oliva, Robert
Gomis, Óscar
Rodríguez-Hernández, P.
Muñoz-Martín, Alfonso
Rodríguez-Mendoza, Ulises R.
Velázquez, M.
Veber, P.
Popescu, Catalina
Manjón, F. J.
author Ibáñez Insa, Jordi
author_facet Ibáñez Insa, Jordi
Sans, Juan Ángel
Cuenca-Gotor, V. P.
Oliva, Robert
Gomis, Óscar
Rodríguez-Hernández, P.
Muñoz-Martín, Alfonso
Rodríguez-Mendoza, Ulises R.
Velázquez, M.
Veber, P.
Popescu, Catalina
Manjón, F. J.
author_role author
author2 Sans, Juan Ángel
Cuenca-Gotor, V. P.
Oliva, Robert
Gomis, Óscar
Rodríguez-Hernández, P.
Muñoz-Martín, Alfonso
Rodríguez-Mendoza, Ulises R.
Velázquez, M.
Veber, P.
Popescu, Catalina
Manjón, F. J.
author2_role author
author
author
author
author
author
author
author
author
author
author
dc.contributor.none.fl_str_mv Generalitat Valenciana
Ministerio de Economía y Competitividad (España)
García-Castellanos, Daniel [0000-0001-8454-8572]
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
dc.subject.none.fl_str_mv Transition Pressure
Neodymium Oxide
Sesquioxides
topic Transition Pressure
Neodymium Oxide
Sesquioxides
description We report a joint experimental and theoretical investigation of the high pressure structural and vibrational properties of terbium sesquioxide (Tb2O3). Powder X-ray diffraction and Raman scattering measurements show that cubic Ia3̅ (C-type) Tb2O3 undergoes two phase transitions up to 25 GPa. We observe a first irreversible reconstructive transition to the monoclinic C2/m (B-type) phase at ∼7 GPa and a subsequent reversible displacive transition from the monoclinic to the trigonal P3̅m1 (A-type) phase at ∼12 GPa. Thus, Tb2O3 is found to follow the well-known C → B → A phase transition sequence found in other cubic rare earth sesquioxides with cations of larger atomic mass than Tb. Our ab initio theoretical calculations predict phase transition pressures and bulk moduli for the three phases in rather good agreement with experimental results. Moreover, Raman-active modes of the three phases have been monitored as a function of pressure, while lattice-dynamics calculations have allowed us to confirm the assignment of the experimental phonon modes in the C- and A-type phases as well as to make a tentative assignment of the symmetry of most vibrational modes in the B-type phase. Finally, we extract the bulk moduli and the Raman-active mode frequencies together with their pressure coefficients for the three phases of Tb2O3. These results are thoroughly compared and discussed in relation to those reported for rare earth and other related sesquioxides as well as with new calculations for selected sesquioxides. It is concluded that the evolution of the volume and bulk modulus of all the three phases of these technologically relevant compounds exhibit a nearly linear trend with respect to the third power of the ionic radii of the cations and that the values of the bulk moduli for the three phases depend on the filling of the f orbitals.
publishDate 2020
dc.date.none.fl_str_mv 2020
2020
2020
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dc.identifier.none.fl_str_mv http://hdl.handle.net/10261/218252
url http://hdl.handle.net/10261/218252
dc.language.none.fl_str_mv Inglés
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https://doi.org/10.1021/acs.inorgchem.0c00834

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spelling Structural and Lattice-Dynamical Properties of Tb2O3 under Compression: A Comparative Study with Rare Earth and Related SesquioxidesIbáñez Insa, JordiSans, Juan ÁngelCuenca-Gotor, V. P.Oliva, RobertGomis, ÓscarRodríguez-Hernández, P.Muñoz-Martín, AlfonsoRodríguez-Mendoza, Ulises R.Velázquez, M.Veber, P.Popescu, CatalinaManjón, F. J.Transition PressureNeodymium OxideSesquioxidesWe report a joint experimental and theoretical investigation of the high pressure structural and vibrational properties of terbium sesquioxide (Tb2O3). Powder X-ray diffraction and Raman scattering measurements show that cubic Ia3̅ (C-type) Tb2O3 undergoes two phase transitions up to 25 GPa. We observe a first irreversible reconstructive transition to the monoclinic C2/m (B-type) phase at ∼7 GPa and a subsequent reversible displacive transition from the monoclinic to the trigonal P3̅m1 (A-type) phase at ∼12 GPa. Thus, Tb2O3 is found to follow the well-known C → B → A phase transition sequence found in other cubic rare earth sesquioxides with cations of larger atomic mass than Tb. Our ab initio theoretical calculations predict phase transition pressures and bulk moduli for the three phases in rather good agreement with experimental results. Moreover, Raman-active modes of the three phases have been monitored as a function of pressure, while lattice-dynamics calculations have allowed us to confirm the assignment of the experimental phonon modes in the C- and A-type phases as well as to make a tentative assignment of the symmetry of most vibrational modes in the B-type phase. Finally, we extract the bulk moduli and the Raman-active mode frequencies together with their pressure coefficients for the three phases of Tb2O3. These results are thoroughly compared and discussed in relation to those reported for rare earth and other related sesquioxides as well as with new calculations for selected sesquioxides. It is concluded that the evolution of the volume and bulk modulus of all the three phases of these technologically relevant compounds exhibit a nearly linear trend with respect to the third power of the ionic radii of the cations and that the values of the bulk moduli for the three phases depend on the filling of the f orbitals.The authors are thankful for the financial support of Generalitat Valenciana under Project PROMETEO 2018/ 123-EFIMAT and of the Spanish Ministerio de Economiá y Competitividad under Projects MAT2015-71035-R, MAT2016-75586-C4-2/3/4-P, and FIS2017-2017-83295-P as well as MALTA Consolider Team research network under project RED2018-102612-T. J.A.S. also acknowledges the Ramón y Cajal program for funding support through RYC- 2015-17482. A.M. and P.R.-H. acknowledge computing time provided by Red Española de Supercomputación (RES) and the MALTA Consolider Team cluster. HP-XRD experiments were performed at MPSD beamline of Alba Synchrotron (experiment no. 2016071772).Peer reviewedACS PublicationsGeneralitat ValencianaMinisterio de Economía y Competitividad (España)García-Castellanos, Daniel [0000-0001-8454-8572]Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]202020202020info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501http://hdl.handle.net/10261/218252reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Inglés#PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE#info:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/MAT2015-71035-Rinfo:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/MAT2016-75586-C4-2-Pinfo:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/FIS2017-83295-Pinfo:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/MAT2016-75586-C4-3-Pinfo:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/MAT2016-75586-C4-4-Phttps://doi.org/10.1021/acs.inorgchem.0c00834Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/2182522026-05-22T06:33:51Z
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