Evidence for a different electronic configuration as a primary effect during compression of orthorhombic perovskites: The case of NdM3+ O3 (M=Cr, Ga)

Marcello Merli, Ardit, Cruciani, Dondi

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Abstract

(Mg,Fe)SiO3 perovskite is the most abundant mineral of the Earth's lower mantle, and compounds with the perovskite structure are perhaps the most widely employed ceramics. Hence, they attract both geophysicists and material scientists. Several investigations attempted to predict their structural evolution at high pressure, and recent advancements highlighted that perovskites having ions with the same formal valence at both polyhedral sites (i.e., 3+:3+) define different compressional patterns when transition metal ions (TMI) are involved. In this study, in situ high-pressure synchrotron XRD measurements coupled with ab initio simulations of the electronic population of NdCrO3 perovskite are compared with the compressional feature of NdGaO3. Almost identical from a steric point of view (Cr3+ and Ga3+ have almost the same ionic radius), the different electronic configuration of octahedrally coordinated ions - which leads to a redistribution of electrons at the 3d orbitals for Cr3+ - allows the crystal field stabilization energy (CFSE) to act as a vehicle of octahedral softening in NdCrO3 or it turns octahedra into rigid units when CFSE is null as in NdGaO3. Besides to highlight that different electronic configurations can act as a primary effect during compression of perovskite compounds, our findings have a deep repercussion on the way the compressibility of perovskites have to be modeled.
Lingua originaleEnglish
Numero di pagine10
RivistaPHYSICAL REVIEW. B
Volume97
Stato di pubblicazionePublished - 2018

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perovskites
Perovskite
crystal field theory
stabilization
configurations
electronics
Stabilization
Ions
softening
Crystals
compressibility
metal ions
vehicles
synchrotrons
ions
Earth mantle
transition metals
Synchrotrons
Compressibility
minerals

All Science Journal Classification (ASJC) codes

  • Electronic, Optical and Magnetic Materials
  • Condensed Matter Physics

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title = "Evidence for a different electronic configuration as a primary effect during compression of orthorhombic perovskites: The case of NdM3+ O3 (M=Cr, Ga)",
abstract = "(Mg,Fe)SiO3 perovskite is the most abundant mineral of the Earth's lower mantle, and compounds with the perovskite structure are perhaps the most widely employed ceramics. Hence, they attract both geophysicists and material scientists. Several investigations attempted to predict their structural evolution at high pressure, and recent advancements highlighted that perovskites having ions with the same formal valence at both polyhedral sites (i.e., 3+:3+) define different compressional patterns when transition metal ions (TMI) are involved. In this study, in situ high-pressure synchrotron XRD measurements coupled with ab initio simulations of the electronic population of NdCrO3 perovskite are compared with the compressional feature of NdGaO3. Almost identical from a steric point of view (Cr3+ and Ga3+ have almost the same ionic radius), the different electronic configuration of octahedrally coordinated ions - which leads to a redistribution of electrons at the 3d orbitals for Cr3+ - allows the crystal field stabilization energy (CFSE) to act as a vehicle of octahedral softening in NdCrO3 or it turns octahedra into rigid units when CFSE is null as in NdGaO3. Besides to highlight that different electronic configurations can act as a primary effect during compression of perovskite compounds, our findings have a deep repercussion on the way the compressibility of perovskites have to be modeled.",
author = "Marcello Merli and Ardit and Cruciani and Dondi",
year = "2018",
language = "English",
volume = "97",
journal = "PHYSICAL REVIEW. B",
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TY - JOUR

T1 - Evidence for a different electronic configuration as a primary effect during compression of orthorhombic perovskites: The case of NdM3+ O3 (M=Cr, Ga)

AU - Merli, Marcello

AU - Ardit, null

AU - Cruciani, null

AU - Dondi, null

PY - 2018

Y1 - 2018

N2 - (Mg,Fe)SiO3 perovskite is the most abundant mineral of the Earth's lower mantle, and compounds with the perovskite structure are perhaps the most widely employed ceramics. Hence, they attract both geophysicists and material scientists. Several investigations attempted to predict their structural evolution at high pressure, and recent advancements highlighted that perovskites having ions with the same formal valence at both polyhedral sites (i.e., 3+:3+) define different compressional patterns when transition metal ions (TMI) are involved. In this study, in situ high-pressure synchrotron XRD measurements coupled with ab initio simulations of the electronic population of NdCrO3 perovskite are compared with the compressional feature of NdGaO3. Almost identical from a steric point of view (Cr3+ and Ga3+ have almost the same ionic radius), the different electronic configuration of octahedrally coordinated ions - which leads to a redistribution of electrons at the 3d orbitals for Cr3+ - allows the crystal field stabilization energy (CFSE) to act as a vehicle of octahedral softening in NdCrO3 or it turns octahedra into rigid units when CFSE is null as in NdGaO3. Besides to highlight that different electronic configurations can act as a primary effect during compression of perovskite compounds, our findings have a deep repercussion on the way the compressibility of perovskites have to be modeled.

AB - (Mg,Fe)SiO3 perovskite is the most abundant mineral of the Earth's lower mantle, and compounds with the perovskite structure are perhaps the most widely employed ceramics. Hence, they attract both geophysicists and material scientists. Several investigations attempted to predict their structural evolution at high pressure, and recent advancements highlighted that perovskites having ions with the same formal valence at both polyhedral sites (i.e., 3+:3+) define different compressional patterns when transition metal ions (TMI) are involved. In this study, in situ high-pressure synchrotron XRD measurements coupled with ab initio simulations of the electronic population of NdCrO3 perovskite are compared with the compressional feature of NdGaO3. Almost identical from a steric point of view (Cr3+ and Ga3+ have almost the same ionic radius), the different electronic configuration of octahedrally coordinated ions - which leads to a redistribution of electrons at the 3d orbitals for Cr3+ - allows the crystal field stabilization energy (CFSE) to act as a vehicle of octahedral softening in NdCrO3 or it turns octahedra into rigid units when CFSE is null as in NdGaO3. Besides to highlight that different electronic configurations can act as a primary effect during compression of perovskite compounds, our findings have a deep repercussion on the way the compressibility of perovskites have to be modeled.

UR - http://hdl.handle.net/10447/327966

UR - https://journals.aps.org/prb/abstract/10.1103/PhysRevB.97.064106

M3 - Article

VL - 97

JO - PHYSICAL REVIEW. B

JF - PHYSICAL REVIEW. B

SN - 2469-9950

ER -