Pressure-induced orbital reordering in Na$_2$CuF$_4$

Fuente: arXiv
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Main Authors: Hiley, Craig I., Crawford, Catriona A., Bull, Craig L., Funnell, Nicholas P., Dey, Urmimala, Bristowe, Nicholas C., Walton, Richard I., Senn, Mark S.
Format: Preprint
Published: 2025
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_version_ 1866910901518467072
author Hiley, Craig I.
Crawford, Catriona A.
Bull, Craig L.
Funnell, Nicholas P.
Dey, Urmimala
Bristowe, Nicholas C.
Walton, Richard I.
Senn, Mark S.
author_facet Hiley, Craig I.
Crawford, Catriona A.
Bull, Craig L.
Funnell, Nicholas P.
Dey, Urmimala
Bristowe, Nicholas C.
Walton, Richard I.
Senn, Mark S.
contents The high-pressure behaviour of Na$_2$CuF$_4$ is explored by powder neutron diffraction and density functional theory (DFT) calculations. A first-order phase transition is observed to take place between 2.4 - 2.9 GPa, involving a reorientation of the Jahn-Teller (JT) long axes of the (CuF6) octahedra (and therefore the d$_{z^2}$ Cu orbitals), in agreement with our DFT calculations which suggest a transition at 2.8 GPa. The transition can be described as being between a state of ferro-orbital order and one of A-type antiferro-orbital order, reflecting a shift in the associated electronic instability from being in the zone-center to zone boundary of the first Brillouin zone of the parent structure, with pressure. This change results in a decoupling of magnitude of the associated Jahn-Teller distortion of the Cu-F bond lengths from the lattice strain. This scenario is supported by our observations that the compressibility of the pre-transition phase is highly anisotropic, whilst in the post-transition phase it becomes almost isotropic, and that we observed no further decrease of the magnitude the JT distortion up to 5 GPa, or melting of the OO in our DFT calculations up to at least 5 GPa.
format Preprint
id arxiv_https___arxiv_org_abs_2504_01120
institution arXiv
publishDate 2025
record_format arxiv
spellingShingle Pressure-induced orbital reordering in Na$_2$CuF$_4$
Hiley, Craig I.
Crawford, Catriona A.
Bull, Craig L.
Funnell, Nicholas P.
Dey, Urmimala
Bristowe, Nicholas C.
Walton, Richard I.
Senn, Mark S.
Strongly Correlated Electrons
Materials Science
The high-pressure behaviour of Na$_2$CuF$_4$ is explored by powder neutron diffraction and density functional theory (DFT) calculations. A first-order phase transition is observed to take place between 2.4 - 2.9 GPa, involving a reorientation of the Jahn-Teller (JT) long axes of the (CuF6) octahedra (and therefore the d$_{z^2}$ Cu orbitals), in agreement with our DFT calculations which suggest a transition at 2.8 GPa. The transition can be described as being between a state of ferro-orbital order and one of A-type antiferro-orbital order, reflecting a shift in the associated electronic instability from being in the zone-center to zone boundary of the first Brillouin zone of the parent structure, with pressure. This change results in a decoupling of magnitude of the associated Jahn-Teller distortion of the Cu-F bond lengths from the lattice strain. This scenario is supported by our observations that the compressibility of the pre-transition phase is highly anisotropic, whilst in the post-transition phase it becomes almost isotropic, and that we observed no further decrease of the magnitude the JT distortion up to 5 GPa, or melting of the OO in our DFT calculations up to at least 5 GPa.
title Pressure-induced orbital reordering in Na$_2$CuF$_4$
topic Strongly Correlated Electrons
Materials Science
url https://arxiv.org/abs/2504.01120