Magnetocrystalline interactions and oxidation state determination of Mn(2−x)V(1+x)O4 (x=0, 1/3 and 1) magnetorresistive spinel family

Autores
Pomiro, Fernando; Ceppi, Sergio Andres; de Paoli, Juan Martin; Sanchez, Rodolfo Daniel; Mesquita, A.; Tirao, German Alfredo; Pannunzio Miner, Elisa Victoria
Año de publicación
2013
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Oxidation states of transition metal cations in spinels-type oxides are sometimes extremely difficult to determine by conventional spectroscopic methods. One of the most complex cases occurs when there are different cations, each one with several possible oxidation states, as in the case of the magnetoresistant Mn(2 x)V(1+x)O4 (x¼0, 1/3 and 1) spinel-type family. In this contribution we describe the determination of the oxidation state of manganese and vanadium in Mn(2 x)V(1+x)O4 (x¼0, 1/3,1) spinel-type compounds by analyzing XANES and high-resolution Kβ X-ray fluorescence spectra. The ionic models found are Mn2+ 2 V4+ O4, Mn2+ 5/3V3.5+ 4/3 O4 and Mn2+V3+ 2 O4. Combination of the present results with previous data provided a reliable cation distribution model. For these spinels, single magnetic electron paramagnetic resonance (EPR) lines are observed at 480 K showing the interaction among the different magnetic ions. The analysis of the EPR parameters show that g-values and relative intensities are highly influenced by the concentration and the high-spin state of Mn2+. EPR broadening linewidth is explained in terms of the bottleneck effect, which is due to the presence of the fast relaxing V3+ ion instead of the weak Mn2+ (S state) coupled to the lattice. The EPR results, at high temperature, are well explained assuming the oxidation states of the magnetic ions obtained by the other spectroscopic techniques.
Fil: Pomiro, Fernando. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Ceppi, Sergio Andres. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Física Enrique Gaviola. Universidad Nacional de Córdoba. Instituto de Física Enrique Gaviola; Argentina
Fil: de Paoli, Juan Martin. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Sanchez, Rodolfo Daniel. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; Argentina. Comisión Nacional de Energía Atómica. Gerencia del Área de Energía Nuclear. Instituto Balseiro; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Mesquita, A.. Universidade Estadual Paulista Julio de Mesquita Filho; Brasil
Fil: Tirao, German Alfredo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Física Enrique Gaviola. Universidad Nacional de Córdoba. Instituto de Física Enrique Gaviola; Argentina
Fil: Pannunzio Miner, Elisa Victoria. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Materia
Cation Distribution
High-Resolution X-Ray Fluorescence
Electron Paramagnetic Resonance
X-Ray Absorption Spectroscopy
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/24999
Acceder
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network_name_str CONICET Digital (CONICET)
spelling Magnetocrystalline interactions and oxidation state determination of Mn(2−x)V(1+x)O4 (x=0, 1/3 and 1) magnetorresistive spinel familyPomiro, FernandoCeppi, Sergio Andresde Paoli, Juan MartinSanchez, Rodolfo DanielMesquita, A.Tirao, German AlfredoPannunzio Miner, Elisa VictoriaCation DistributionHigh-Resolution X-Ray FluorescenceElectron Paramagnetic ResonanceX-Ray Absorption Spectroscopyhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Oxidation states of transition metal cations in spinels-type oxides are sometimes extremely difficult to determine by conventional spectroscopic methods. One of the most complex cases occurs when there are different cations, each one with several possible oxidation states, as in the case of the magnetoresistant Mn(2 x)V(1+x)O4 (x¼0, 1/3 and 1) spinel-type family. In this contribution we describe the determination of the oxidation state of manganese and vanadium in Mn(2 x)V(1+x)O4 (x¼0, 1/3,1) spinel-type compounds by analyzing XANES and high-resolution Kβ X-ray fluorescence spectra. The ionic models found are Mn2+ 2 V4+ O4, Mn2+ 5/3V3.5+ 4/3 O4 and Mn2+V3+ 2 O4. Combination of the present results with previous data provided a reliable cation distribution model. For these spinels, single magnetic electron paramagnetic resonance (EPR) lines are observed at 480 K showing the interaction among the different magnetic ions. The analysis of the EPR parameters show that g-values and relative intensities are highly influenced by the concentration and the high-spin state of Mn2+. EPR broadening linewidth is explained in terms of the bottleneck effect, which is due to the presence of the fast relaxing V3+ ion instead of the weak Mn2+ (S state) coupled to the lattice. The EPR results, at high temperature, are well explained assuming the oxidation states of the magnetic ions obtained by the other spectroscopic techniques.Fil: Pomiro, Fernando. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Ceppi, Sergio Andres. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Física Enrique Gaviola. Universidad Nacional de Córdoba. Instituto de Física Enrique Gaviola; ArgentinaFil: de Paoli, Juan Martin. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Sanchez, Rodolfo Daniel. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; Argentina. Comisión Nacional de Energía Atómica. Gerencia del Área de Energía Nuclear. Instituto Balseiro; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Mesquita, A.. Universidade Estadual Paulista Julio de Mesquita Filho; BrasilFil: Tirao, German Alfredo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Física Enrique Gaviola. Universidad Nacional de Córdoba. Instituto de Física Enrique Gaviola; ArgentinaFil: Pannunzio Miner, Elisa Victoria. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaElsevier Inc2013-07info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/24999Pomiro, Fernando; Ceppi, Sergio Andres; de Paoli, Juan Martin; Sanchez, Rodolfo Daniel; Mesquita, A.; et al.; Magnetocrystalline interactions and oxidation state determination of Mn(2−x)V(1+x)O4 (x=0, 1/3 and 1) magnetorresistive spinel family; Elsevier Inc; Journal of Solid State Chemistry; 205; 7-2013; 57-630022-4596CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1016/j.jssc.2013.06.025info:eu-repo/semantics/altIdentifier/url/http://www.sciencedirect.com/science/article/pii/S0022459613003174info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-nd/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-11-12T09:35:01Zoai:ri.conicet.gov.ar:11336/24999instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-11-12 09:35:01.94CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Magnetocrystalline interactions and oxidation state determination of Mn(2−x)V(1+x)O4 (x=0, 1/3 and 1) magnetorresistive spinel family
title Magnetocrystalline interactions and oxidation state determination of Mn(2−x)V(1+x)O4 (x=0, 1/3 and 1) magnetorresistive spinel family
spellingShingle Magnetocrystalline interactions and oxidation state determination of Mn(2−x)V(1+x)O4 (x=0, 1/3 and 1) magnetorresistive spinel family
Pomiro, Fernando
Cation Distribution
High-Resolution X-Ray Fluorescence
Electron Paramagnetic Resonance
X-Ray Absorption Spectroscopy
title_short Magnetocrystalline interactions and oxidation state determination of Mn(2−x)V(1+x)O4 (x=0, 1/3 and 1) magnetorresistive spinel family
title_full Magnetocrystalline interactions and oxidation state determination of Mn(2−x)V(1+x)O4 (x=0, 1/3 and 1) magnetorresistive spinel family
title_fullStr Magnetocrystalline interactions and oxidation state determination of Mn(2−x)V(1+x)O4 (x=0, 1/3 and 1) magnetorresistive spinel family
title_full_unstemmed Magnetocrystalline interactions and oxidation state determination of Mn(2−x)V(1+x)O4 (x=0, 1/3 and 1) magnetorresistive spinel family
title_sort Magnetocrystalline interactions and oxidation state determination of Mn(2−x)V(1+x)O4 (x=0, 1/3 and 1) magnetorresistive spinel family
dc.creator.none.fl_str_mv Pomiro, Fernando
Ceppi, Sergio Andres
de Paoli, Juan Martin
Sanchez, Rodolfo Daniel
Mesquita, A.
Tirao, German Alfredo
Pannunzio Miner, Elisa Victoria
author Pomiro, Fernando
author_facet Pomiro, Fernando
Ceppi, Sergio Andres
de Paoli, Juan Martin
Sanchez, Rodolfo Daniel
Mesquita, A.
Tirao, German Alfredo
Pannunzio Miner, Elisa Victoria
author_role author
author2 Ceppi, Sergio Andres
de Paoli, Juan Martin
Sanchez, Rodolfo Daniel
Mesquita, A.
Tirao, German Alfredo
Pannunzio Miner, Elisa Victoria
author2_role author
author
author
author
author
author
dc.subject.none.fl_str_mv Cation Distribution
High-Resolution X-Ray Fluorescence
Electron Paramagnetic Resonance
X-Ray Absorption Spectroscopy
topic Cation Distribution
High-Resolution X-Ray Fluorescence
Electron Paramagnetic Resonance
X-Ray Absorption Spectroscopy
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Oxidation states of transition metal cations in spinels-type oxides are sometimes extremely difficult to determine by conventional spectroscopic methods. One of the most complex cases occurs when there are different cations, each one with several possible oxidation states, as in the case of the magnetoresistant Mn(2 x)V(1+x)O4 (x¼0, 1/3 and 1) spinel-type family. In this contribution we describe the determination of the oxidation state of manganese and vanadium in Mn(2 x)V(1+x)O4 (x¼0, 1/3,1) spinel-type compounds by analyzing XANES and high-resolution Kβ X-ray fluorescence spectra. The ionic models found are Mn2+ 2 V4+ O4, Mn2+ 5/3V3.5+ 4/3 O4 and Mn2+V3+ 2 O4. Combination of the present results with previous data provided a reliable cation distribution model. For these spinels, single magnetic electron paramagnetic resonance (EPR) lines are observed at 480 K showing the interaction among the different magnetic ions. The analysis of the EPR parameters show that g-values and relative intensities are highly influenced by the concentration and the high-spin state of Mn2+. EPR broadening linewidth is explained in terms of the bottleneck effect, which is due to the presence of the fast relaxing V3+ ion instead of the weak Mn2+ (S state) coupled to the lattice. The EPR results, at high temperature, are well explained assuming the oxidation states of the magnetic ions obtained by the other spectroscopic techniques.
Fil: Pomiro, Fernando. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Ceppi, Sergio Andres. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Física Enrique Gaviola. Universidad Nacional de Córdoba. Instituto de Física Enrique Gaviola; Argentina
Fil: de Paoli, Juan Martin. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Sanchez, Rodolfo Daniel. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; Argentina. Comisión Nacional de Energía Atómica. Gerencia del Área de Energía Nuclear. Instituto Balseiro; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Mesquita, A.. Universidade Estadual Paulista Julio de Mesquita Filho; Brasil
Fil: Tirao, German Alfredo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Física Enrique Gaviola. Universidad Nacional de Córdoba. Instituto de Física Enrique Gaviola; Argentina
Fil: Pannunzio Miner, Elisa Victoria. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
description Oxidation states of transition metal cations in spinels-type oxides are sometimes extremely difficult to determine by conventional spectroscopic methods. One of the most complex cases occurs when there are different cations, each one with several possible oxidation states, as in the case of the magnetoresistant Mn(2 x)V(1+x)O4 (x¼0, 1/3 and 1) spinel-type family. In this contribution we describe the determination of the oxidation state of manganese and vanadium in Mn(2 x)V(1+x)O4 (x¼0, 1/3,1) spinel-type compounds by analyzing XANES and high-resolution Kβ X-ray fluorescence spectra. The ionic models found are Mn2+ 2 V4+ O4, Mn2+ 5/3V3.5+ 4/3 O4 and Mn2+V3+ 2 O4. Combination of the present results with previous data provided a reliable cation distribution model. For these spinels, single magnetic electron paramagnetic resonance (EPR) lines are observed at 480 K showing the interaction among the different magnetic ions. The analysis of the EPR parameters show that g-values and relative intensities are highly influenced by the concentration and the high-spin state of Mn2+. EPR broadening linewidth is explained in terms of the bottleneck effect, which is due to the presence of the fast relaxing V3+ ion instead of the weak Mn2+ (S state) coupled to the lattice. The EPR results, at high temperature, are well explained assuming the oxidation states of the magnetic ions obtained by the other spectroscopic techniques.
publishDate 2013
dc.date.none.fl_str_mv 2013-07
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/24999
Pomiro, Fernando; Ceppi, Sergio Andres; de Paoli, Juan Martin; Sanchez, Rodolfo Daniel; Mesquita, A.; et al.; Magnetocrystalline interactions and oxidation state determination of Mn(2−x)V(1+x)O4 (x=0, 1/3 and 1) magnetorresistive spinel family; Elsevier Inc; Journal of Solid State Chemistry; 205; 7-2013; 57-63
0022-4596
CONICET Digital
CONICET
url http://hdl.handle.net/11336/24999
identifier_str_mv Pomiro, Fernando; Ceppi, Sergio Andres; de Paoli, Juan Martin; Sanchez, Rodolfo Daniel; Mesquita, A.; et al.; Magnetocrystalline interactions and oxidation state determination of Mn(2−x)V(1+x)O4 (x=0, 1/3 and 1) magnetorresistive spinel family; Elsevier Inc; Journal of Solid State Chemistry; 205; 7-2013; 57-63
0022-4596
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
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info:eu-repo/semantics/altIdentifier/url/http://www.sciencedirect.com/science/article/pii/S0022459613003174
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
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eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
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dc.publisher.none.fl_str_mv Elsevier Inc
publisher.none.fl_str_mv Elsevier Inc
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repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
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