Origin of the ESR spectrum in the Prussian blue analog RbMn[Fe(CN)(6)]center dot H2O

A. Antal; A. Janossy; L. Forro; E. J. M. Vertelman; P. J. van Koningsbruggen; P. H. M. van Loosdrecht

doi:10.1103/PhysRevB.82.014422

Origin of the ESR spectrum in the Prussian blue analog RbMn[Fe(CN)(6)]center dot H2O

A. Antal^*, A. Janossy, L. Forro, E. J. M. Vertelman, P. J. van Koningsbruggen, P. H. M. van Loosdrecht

^*Corresponding author for this work

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Abstract

We present an electron spin resonance (ESR) study at excitation frequencies of 9.4 and 222.4 GHz of powders and single crystals of a Prussian blue analog (PBA), RbMn[Fe(CN)(6)]center dot H2O in which Fe and Mn undergoes a charge-transfer transition between 175 and 300 K. The ESR of PBA powders, also reported by Pregelj et al. [J. Magn. Magn. Mater. 316, e680 (2007)], is assigned to cubic magnetic clusters of Mn2+ ions surrounding Fe (CN)(6) vacancies. The clusters are well isolated from the bulk and are superparamagnetic below 50 K. In single crystals, various defects with lower symmetry are also observed. Spin-lattice relaxation broadens the bulk ESR beyond observability. This strong spin relaxation is unexpected above the charge-transfer transition and is attributed to a mixing of the Mn3+-Fe2+ state into the prevalent Mn2+-Fe3+ state.

Original language	English
Article number	014422
Pages (from-to)	014422-1-014422-5
Number of pages	5
Journal	Physical Review. B: Condensed Matter and Materials Physics
Volume	82
Issue number	1
DOIs	https://doi.org/10.1103/PhysRevB.82.014422
Publication status	Published - 22-Jul-2010

Keywords

RUBIDIUM MANGANESE HEXACYANOFERRATE
ELECTRON-TRANSFER

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title = "Origin of the ESR spectrum in the Prussian blue analog RbMn[Fe(CN)(6)]center dot H2O",

abstract = "We present an electron spin resonance (ESR) study at excitation frequencies of 9.4 and 222.4 GHz of powders and single crystals of a Prussian blue analog (PBA), RbMn[Fe(CN)(6)]center dot H2O in which Fe and Mn undergoes a charge-transfer transition between 175 and 300 K. The ESR of PBA powders, also reported by Pregelj et al. [J. Magn. Magn. Mater. 316, e680 (2007)], is assigned to cubic magnetic clusters of Mn2+ ions surrounding Fe (CN)(6) vacancies. The clusters are well isolated from the bulk and are superparamagnetic below 50 K. In single crystals, various defects with lower symmetry are also observed. Spin-lattice relaxation broadens the bulk ESR beyond observability. This strong spin relaxation is unexpected above the charge-transfer transition and is attributed to a mixing of the Mn3+-Fe2+ state into the prevalent Mn2+-Fe3+ state.",

keywords = "RUBIDIUM MANGANESE HEXACYANOFERRATE, ELECTRON-TRANSFER",

author = "A. Antal and A. Janossy and L. Forro and Vertelman, {E. J. M.} and {van Koningsbruggen}, {P. J.} and {van Loosdrecht}, {P. H. M.}",

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T1 - Origin of the ESR spectrum in the Prussian blue analog RbMn[Fe(CN)(6)]center dot H2O

AU - Antal, A.

AU - Janossy, A.

AU - Forro, L.

AU - Vertelman, E. J. M.

AU - van Koningsbruggen, P. J.

AU - van Loosdrecht, P. H. M.

PY - 2010/7/22

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N2 - We present an electron spin resonance (ESR) study at excitation frequencies of 9.4 and 222.4 GHz of powders and single crystals of a Prussian blue analog (PBA), RbMn[Fe(CN)(6)]center dot H2O in which Fe and Mn undergoes a charge-transfer transition between 175 and 300 K. The ESR of PBA powders, also reported by Pregelj et al. [J. Magn. Magn. Mater. 316, e680 (2007)], is assigned to cubic magnetic clusters of Mn2+ ions surrounding Fe (CN)(6) vacancies. The clusters are well isolated from the bulk and are superparamagnetic below 50 K. In single crystals, various defects with lower symmetry are also observed. Spin-lattice relaxation broadens the bulk ESR beyond observability. This strong spin relaxation is unexpected above the charge-transfer transition and is attributed to a mixing of the Mn3+-Fe2+ state into the prevalent Mn2+-Fe3+ state.

AB - We present an electron spin resonance (ESR) study at excitation frequencies of 9.4 and 222.4 GHz of powders and single crystals of a Prussian blue analog (PBA), RbMn[Fe(CN)(6)]center dot H2O in which Fe and Mn undergoes a charge-transfer transition between 175 and 300 K. The ESR of PBA powders, also reported by Pregelj et al. [J. Magn. Magn. Mater. 316, e680 (2007)], is assigned to cubic magnetic clusters of Mn2+ ions surrounding Fe (CN)(6) vacancies. The clusters are well isolated from the bulk and are superparamagnetic below 50 K. In single crystals, various defects with lower symmetry are also observed. Spin-lattice relaxation broadens the bulk ESR beyond observability. This strong spin relaxation is unexpected above the charge-transfer transition and is attributed to a mixing of the Mn3+-Fe2+ state into the prevalent Mn2+-Fe3+ state.

KW - RUBIDIUM MANGANESE HEXACYANOFERRATE

KW - ELECTRON-TRANSFER

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JO - Physical Review. B: Condensed Matter and Materials Physics

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