Spin-orbit coupling and Jahn-Teller distortion in bimetallic oxalates

Randy S. Fishman; Satoshi Okamoto; Fernando A. Reboredo

doi:10.1016/j.poly.2008.11.007

Spin-orbit coupling and Jahn-Teller distortion in bimetallic oxalates

Randy S. Fishman, Satoshi Okamoto, Fernando A. Reboredo

Materials Theory

Research output: Contribution to journal › Article › peer-review

5 Scopus citations

Abstract

The C₃-symmetric crystal-field potential in the Fe(II)Fe(III) bimetallic oxalates splits the L = 2 Fe(II) multiplet into two doublets and one singlet. In compounds that exhibit magnetic compensation, one of the doublets lies lowest in energy and carries an average orbital angular momentum L_z^cf that exceeds a threshold value of roughly 0.25. In a range of L_z^cf, a Jahn-Teller (JT) distortion enhances the splitting of the low-lying doublet and breaks the C₃ symmetry of the bimetallic planes around the ferrimagnetic transition temperature. Due to the competition with the spin-orbit coupling, the JT distortion disappears at low temperatures in compounds that display magnetic compensation. A comparison with recent measurements provides compelling evidence for this inverse, low-temperature JT transition. The size of the JT distortion is estimated using first-principles calculations, which suggest that the long-range ordering of smaller, non-C₃-symmetric organic cations can eliminate magnetic compensation.

Original language	English
Pages (from-to)	1740-1745
Number of pages	6
Journal	Polyhedron
Volume	28
Issue number	9-10
DOIs	https://doi.org/10.1016/j.poly.2008.11.007
State	Published - Jun 22 2009

Funding

We would like to acknowledge conversations with Dr. Murilo Tiago. This research was sponsored by the Laboratory Directed Research and Development Program of Oak Ridge National Laboratory, managed by UT-Battelle, LLC for the US Department of Energy under Contract No. DE-AC05-00OR22725 and by the Division of Materials Science and Engineering of the US DOE.

Funders	Funder number
Division of Materials Science and Engineering
US Department of Energy	DE-AC05-00OR22725
UT-Battelle
U.S. Department of Energy
Oak Ridge National Laboratory

Keywords

Bimetallic oxalates
Crystal fields
Jahn-Teller distortion
Spin-orbit interaction

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title = "Spin-orbit coupling and Jahn-Teller distortion in bimetallic oxalates",

abstract = "The C3-symmetric crystal-field potential in the Fe(II)Fe(III) bimetallic oxalates splits the L = 2 Fe(II) multiplet into two doublets and one singlet. In compounds that exhibit magnetic compensation, one of the doublets lies lowest in energy and carries an average orbital angular momentum Lzcf that exceeds a threshold value of roughly 0.25. In a range of Lzcf, a Jahn-Teller (JT) distortion enhances the splitting of the low-lying doublet and breaks the C3 symmetry of the bimetallic planes around the ferrimagnetic transition temperature. Due to the competition with the spin-orbit coupling, the JT distortion disappears at low temperatures in compounds that display magnetic compensation. A comparison with recent measurements provides compelling evidence for this inverse, low-temperature JT transition. The size of the JT distortion is estimated using first-principles calculations, which suggest that the long-range ordering of smaller, non-C3-symmetric organic cations can eliminate magnetic compensation.",

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AU - Fishman, Randy S.

AU - Okamoto, Satoshi

AU - Reboredo, Fernando A.

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N2 - The C3-symmetric crystal-field potential in the Fe(II)Fe(III) bimetallic oxalates splits the L = 2 Fe(II) multiplet into two doublets and one singlet. In compounds that exhibit magnetic compensation, one of the doublets lies lowest in energy and carries an average orbital angular momentum Lzcf that exceeds a threshold value of roughly 0.25. In a range of Lzcf, a Jahn-Teller (JT) distortion enhances the splitting of the low-lying doublet and breaks the C3 symmetry of the bimetallic planes around the ferrimagnetic transition temperature. Due to the competition with the spin-orbit coupling, the JT distortion disappears at low temperatures in compounds that display magnetic compensation. A comparison with recent measurements provides compelling evidence for this inverse, low-temperature JT transition. The size of the JT distortion is estimated using first-principles calculations, which suggest that the long-range ordering of smaller, non-C3-symmetric organic cations can eliminate magnetic compensation.

AB - The C3-symmetric crystal-field potential in the Fe(II)Fe(III) bimetallic oxalates splits the L = 2 Fe(II) multiplet into two doublets and one singlet. In compounds that exhibit magnetic compensation, one of the doublets lies lowest in energy and carries an average orbital angular momentum Lzcf that exceeds a threshold value of roughly 0.25. In a range of Lzcf, a Jahn-Teller (JT) distortion enhances the splitting of the low-lying doublet and breaks the C3 symmetry of the bimetallic planes around the ferrimagnetic transition temperature. Due to the competition with the spin-orbit coupling, the JT distortion disappears at low temperatures in compounds that display magnetic compensation. A comparison with recent measurements provides compelling evidence for this inverse, low-temperature JT transition. The size of the JT distortion is estimated using first-principles calculations, which suggest that the long-range ordering of smaller, non-C3-symmetric organic cations can eliminate magnetic compensation.

KW - Bimetallic oxalates

KW - Crystal fields

KW - Jahn-Teller distortion

KW - Spin-orbit interaction

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JO - Polyhedron

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IS - 9-10

ER -

Spin-orbit coupling and Jahn-Teller distortion in bimetallic oxalates

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