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
- Institución
- Universidad Nacional de La Plata
- OAI Identificador
- oai:sedici.unlp.edu.ar:10915/133527
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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 |
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