Far- and mid-infrared emission and reflectivity of orthorhombic and cubic ErMn O 3: Polarons and bipolarons

Autores
Massa, Néstor Emilio; del Campo, Leire; Holldack, Karsten; Phuoc, Vinh Ta; Echegut, Patrick; Kayser, Paula; Alonso, José Antonio
Año de publicación
2018
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
We report on the high-temperature evolution of far- and mid-infrared reflectivity and emissivity spectra of ambient orthorhombic ErMnO3 from 12 K to sample decomposition above 1800 K. At low temperatures the number of phonons agrees with the predictions for orthorhombic space group D2h16-Pbnm (Z=4) and coexists with a paramagnon spin resonance and rare-earth crystal-field transitions. Increasing the temperature, a number of vibrational bands undergo profile broadening and softening approaching the orbital disordered phase where the orthorhombic Ó lower-temperature cooperative phase coexists with cubic-orthorhombic O. O-ErMnO3 undergoes a first-order order-disorder transition into the perovskite cubic phase at Tcubic∼1329K±20K where the three triple degenerate phonons allowed by the space group Pm-3m (Z=1) are identified. At about 800 K, a quantitative small polaron analysis of the orthorhombic midinfrared real part optical conductivity shows that antisymmetric and symmetric breathing modes sustain the strongest electron-phonon interactions. Above Tcubic the bipolaron fingerprint profile is the midinfrared dominant and only feature. Its appearance correlates with the localized screening of the highest vibrational mode reststrahlen band. We propose that the longitudinal optical mode macroscopic field screening is a consequence of dynamically sharing δ disproportioned eg electrons hovering over the Jahn-Teller distorted octahedral dimer {Mn(QJT)3+δ[Mn(QJT)[3]-δ]O6/2}2. A thermal driven insulator-metal transition is detected with onset ∼1600 K. We also address the occurrence of an inhomogeneity induced terahertz band result of heating the samples in dry air, triggering Mn3+-Mn4+ double exchange, under the presence of Mn4+ smaller ions stabilizing the orthorhombic lattice.
Centro de Química Inorgánica
Materia
Química
Binary alloys
Electron spin resonance spectroscopy
Electron-phonon interactions
Infrared devices
Optical conductivity
Orbits
Perovskite
Polarons
Rare earths
Reflection
Nivel de accesibilidad
acceso abierto
Condiciones de uso
http://creativecommons.org/licenses/by/4.0/
Repositorio
SEDICI (UNLP)
Institución
Universidad Nacional de La Plata
OAI Identificador
oai:sedici.unlp.edu.ar:10915/133527

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oai_identifier_str oai:sedici.unlp.edu.ar:10915/133527
network_acronym_str SEDICI
repository_id_str 1329
network_name_str SEDICI (UNLP)
spelling Far- and mid-infrared emission and reflectivity of orthorhombic and cubic ErMn O 3: Polarons and bipolaronsMassa, Néstor Emiliodel Campo, LeireHolldack, KarstenPhuoc, Vinh TaEchegut, PatrickKayser, PaulaAlonso, José AntonioQuímicaBinary alloysElectron spin resonance spectroscopyElectron-phonon interactionsInfrared devicesOptical conductivityOrbitsPerovskitePolaronsRare earthsReflectionWe report on the high-temperature evolution of far- and mid-infrared reflectivity and emissivity spectra of ambient orthorhombic ErMnO3 from 12 K to sample decomposition above 1800 K. At low temperatures the number of phonons agrees with the predictions for orthorhombic space group D2h16-Pbnm (Z=4) and coexists with a paramagnon spin resonance and rare-earth crystal-field transitions. Increasing the temperature, a number of vibrational bands undergo profile broadening and softening approaching the orbital disordered phase where the orthorhombic Ó lower-temperature cooperative phase coexists with cubic-orthorhombic O. O-ErMnO3 undergoes a first-order order-disorder transition into the perovskite cubic phase at Tcubic∼1329K±20K where the three triple degenerate phonons allowed by the space group Pm-3m (Z=1) are identified. At about 800 K, a quantitative small polaron analysis of the orthorhombic midinfrared real part optical conductivity shows that antisymmetric and symmetric breathing modes sustain the strongest electron-phonon interactions. Above Tcubic the bipolaron fingerprint profile is the midinfrared dominant and only feature. Its appearance correlates with the localized screening of the highest vibrational mode reststrahlen band. We propose that the longitudinal optical mode macroscopic field screening is a consequence of dynamically sharing δ disproportioned eg electrons hovering over the Jahn-Teller distorted octahedral dimer {Mn(QJT)3+δ[Mn(QJT)[3]-δ]O6/2}2. A thermal driven insulator-metal transition is detected with onset ∼1600 K. We also address the occurrence of an inhomogeneity induced terahertz band result of heating the samples in dry air, triggering Mn3+-Mn4+ double exchange, under the presence of Mn4+ smaller ions stabilizing the orthorhombic lattice.Centro de Química Inorgánica2018-11-09info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionArticulohttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfhttp://sedici.unlp.edu.ar/handle/10915/133527enginfo:eu-repo/semantics/altIdentifier/issn/2469-9950info:eu-repo/semantics/altIdentifier/issn/2469-9969info:eu-repo/semantics/altIdentifier/doi/10.1103/physrevb.98.184302info:eu-repo/semantics/altIdentifier/arxiv/1811.04694info:eu-repo/semantics/openAccesshttp://creativecommons.org/licenses/by/4.0/Creative Commons Attribution 4.0 International (CC BY 4.0)reponame:SEDICI (UNLP)instname:Universidad Nacional de La Platainstacron:UNLP2025-09-29T11:31:47Zoai:sedici.unlp.edu.ar:10915/133527Institucionalhttp://sedici.unlp.edu.ar/Universidad públicaNo correspondehttp://sedici.unlp.edu.ar/oai/snrdalira@sedici.unlp.edu.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:13292025-09-29 11:31:47.262SEDICI (UNLP) - Universidad Nacional de La Platafalse
dc.title.none.fl_str_mv Far- and mid-infrared emission and reflectivity of orthorhombic and cubic ErMn O 3: Polarons and bipolarons
title Far- and mid-infrared emission and reflectivity of orthorhombic and cubic ErMn O 3: Polarons and bipolarons
spellingShingle Far- and mid-infrared emission and reflectivity of orthorhombic and cubic ErMn O 3: Polarons and bipolarons
Massa, Néstor Emilio
Química
Binary alloys
Electron spin resonance spectroscopy
Electron-phonon interactions
Infrared devices
Optical conductivity
Orbits
Perovskite
Polarons
Rare earths
Reflection
title_short Far- and mid-infrared emission and reflectivity of orthorhombic and cubic ErMn O 3: Polarons and bipolarons
title_full Far- and mid-infrared emission and reflectivity of orthorhombic and cubic ErMn O 3: Polarons and bipolarons
title_fullStr Far- and mid-infrared emission and reflectivity of orthorhombic and cubic ErMn O 3: Polarons and bipolarons
title_full_unstemmed Far- and mid-infrared emission and reflectivity of orthorhombic and cubic ErMn O 3: Polarons and bipolarons
title_sort Far- and mid-infrared emission and reflectivity of orthorhombic and cubic ErMn O 3: Polarons and bipolarons
dc.creator.none.fl_str_mv Massa, Néstor Emilio
del Campo, Leire
Holldack, Karsten
Phuoc, Vinh Ta
Echegut, Patrick
Kayser, Paula
Alonso, José Antonio
author Massa, Néstor Emilio
author_facet Massa, Néstor Emilio
del Campo, Leire
Holldack, Karsten
Phuoc, Vinh Ta
Echegut, Patrick
Kayser, Paula
Alonso, José Antonio
author_role author
author2 del Campo, Leire
Holldack, Karsten
Phuoc, Vinh Ta
Echegut, Patrick
Kayser, Paula
Alonso, José Antonio
author2_role author
author
author
author
author
author
dc.subject.none.fl_str_mv Química
Binary alloys
Electron spin resonance spectroscopy
Electron-phonon interactions
Infrared devices
Optical conductivity
Orbits
Perovskite
Polarons
Rare earths
Reflection
topic Química
Binary alloys
Electron spin resonance spectroscopy
Electron-phonon interactions
Infrared devices
Optical conductivity
Orbits
Perovskite
Polarons
Rare earths
Reflection
dc.description.none.fl_txt_mv We report on the high-temperature evolution of far- and mid-infrared reflectivity and emissivity spectra of ambient orthorhombic ErMnO3 from 12 K to sample decomposition above 1800 K. At low temperatures the number of phonons agrees with the predictions for orthorhombic space group D2h16-Pbnm (Z=4) and coexists with a paramagnon spin resonance and rare-earth crystal-field transitions. Increasing the temperature, a number of vibrational bands undergo profile broadening and softening approaching the orbital disordered phase where the orthorhombic Ó lower-temperature cooperative phase coexists with cubic-orthorhombic O. O-ErMnO3 undergoes a first-order order-disorder transition into the perovskite cubic phase at Tcubic∼1329K±20K where the three triple degenerate phonons allowed by the space group Pm-3m (Z=1) are identified. At about 800 K, a quantitative small polaron analysis of the orthorhombic midinfrared real part optical conductivity shows that antisymmetric and symmetric breathing modes sustain the strongest electron-phonon interactions. Above Tcubic the bipolaron fingerprint profile is the midinfrared dominant and only feature. Its appearance correlates with the localized screening of the highest vibrational mode reststrahlen band. We propose that the longitudinal optical mode macroscopic field screening is a consequence of dynamically sharing δ disproportioned eg electrons hovering over the Jahn-Teller distorted octahedral dimer {Mn(QJT)3+δ[Mn(QJT)[3]-δ]O6/2}2. A thermal driven insulator-metal transition is detected with onset ∼1600 K. We also address the occurrence of an inhomogeneity induced terahertz band result of heating the samples in dry air, triggering Mn3+-Mn4+ double exchange, under the presence of Mn4+ smaller ions stabilizing the orthorhombic lattice.
Centro de Química Inorgánica
description We report on the high-temperature evolution of far- and mid-infrared reflectivity and emissivity spectra of ambient orthorhombic ErMnO3 from 12 K to sample decomposition above 1800 K. At low temperatures the number of phonons agrees with the predictions for orthorhombic space group D2h16-Pbnm (Z=4) and coexists with a paramagnon spin resonance and rare-earth crystal-field transitions. Increasing the temperature, a number of vibrational bands undergo profile broadening and softening approaching the orbital disordered phase where the orthorhombic Ó lower-temperature cooperative phase coexists with cubic-orthorhombic O. O-ErMnO3 undergoes a first-order order-disorder transition into the perovskite cubic phase at Tcubic∼1329K±20K where the three triple degenerate phonons allowed by the space group Pm-3m (Z=1) are identified. At about 800 K, a quantitative small polaron analysis of the orthorhombic midinfrared real part optical conductivity shows that antisymmetric and symmetric breathing modes sustain the strongest electron-phonon interactions. Above Tcubic the bipolaron fingerprint profile is the midinfrared dominant and only feature. Its appearance correlates with the localized screening of the highest vibrational mode reststrahlen band. We propose that the longitudinal optical mode macroscopic field screening is a consequence of dynamically sharing δ disproportioned eg electrons hovering over the Jahn-Teller distorted octahedral dimer {Mn(QJT)3+δ[Mn(QJT)[3]-δ]O6/2}2. A thermal driven insulator-metal transition is detected with onset ∼1600 K. We also address the occurrence of an inhomogeneity induced terahertz band result of heating the samples in dry air, triggering Mn3+-Mn4+ double exchange, under the presence of Mn4+ smaller ions stabilizing the orthorhombic lattice.
publishDate 2018
dc.date.none.fl_str_mv 2018-11-09
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
Articulo
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://sedici.unlp.edu.ar/handle/10915/133527
url http://sedici.unlp.edu.ar/handle/10915/133527
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/issn/2469-9950
info:eu-repo/semantics/altIdentifier/issn/2469-9969
info:eu-repo/semantics/altIdentifier/doi/10.1103/physrevb.98.184302
info:eu-repo/semantics/altIdentifier/arxiv/1811.04694
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
http://creativecommons.org/licenses/by/4.0/
Creative Commons Attribution 4.0 International (CC BY 4.0)
eu_rights_str_mv openAccess
rights_invalid_str_mv http://creativecommons.org/licenses/by/4.0/
Creative Commons Attribution 4.0 International (CC BY 4.0)
dc.format.none.fl_str_mv application/pdf
dc.source.none.fl_str_mv reponame:SEDICI (UNLP)
instname:Universidad Nacional de La Plata
instacron:UNLP
reponame_str SEDICI (UNLP)
collection SEDICI (UNLP)
instname_str Universidad Nacional de La Plata
instacron_str UNLP
institution UNLP
repository.name.fl_str_mv SEDICI (UNLP) - Universidad Nacional de La Plata
repository.mail.fl_str_mv alira@sedici.unlp.edu.ar
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