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Carver G, Dobe C, Jensen TB, et al. Spectroscopic, magnetochemical, and crystallographic study of cesium iron phosphate hexahydrate: characterization of the electronic structure of the iron(II) hexa-aqua cation in a quasicubic environment. Inorg Chem. 2006;45(12):4695-705doi: 10.1021/ic0601889.
Carver, G., Dobe, C., Jensen, T. B., Tregenna-Piggott, P. L., Janssen, S., Bill, E., McIntyre, G. J., & Barra, A. L. (2006). Spectroscopic, magnetochemical, and crystallographic study of cesium iron phosphate hexahydrate: characterization of the electronic structure of the iron(II) hexa-aqua cation in a quasicubic environment. Inorganic chemistry, 45(12), 4695-705. https://doi.org/10.1021/ic0601889
Carver, Graham, et al. "Spectroscopic, magnetochemical, and crystallographic study of cesium iron phosphate hexahydrate: characterization of the electronic structure of the iron(II) hexa-aqua cation in a quasicubic environment." Inorganic chemistry vol. 45,12 (2006): 4695-705. doi: https://doi.org/10.1021/ic0601889
Carver G, Dobe C, Jensen TB, Tregenna-Piggott PL, Janssen S, Bill E, McIntyre GJ, Barra AL. Spectroscopic, magnetochemical, and crystallographic study of cesium iron phosphate hexahydrate: characterization of the electronic structure of the iron(II) hexa-aqua cation in a quasicubic environment. Inorg Chem. 2006 Jun 12;45(12):4695-705. doi: 10.1021/ic0601889. PMID: 16749833.
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Inorg Chem. 2006 Jun 12;45(12):4695-705. doi: 10.1021/ic0601889.

Spectroscopic, magnetochemical, and crystallographic study of cesium iron phosphate hexahydrate: characterization of the electronic structure of the iron(II) hexa-aqua cation in a quasicubic environment.

Inorganic chemistry

Graham Carver, Christopher Dobe, Thomas B Jensen, Philip L W Tregenna-Piggott, Stefan Janssen, Eckhard Bill, Garry J McIntyre, Anne-Laure Barra

Affiliations

  1. Department of Chemistry and Biochemistry, University of Bern, Freiestrasse 3, 3012 Bern, Switzerland.

PMID: 16749833 DOI: 10.1021/ic0601889

Abstract

Spectroscopic, magnetochemical, and crystallographic data are presented for CsFe(H2O)6PO4, a member of a little-known isomorphous series of salts that facilitates the study of hexa-aqua ions in a quasicubic environment. Above 120 K, the deviations from cubic symmetry are minimal, as shown by the first example of an iron(II) Mössbauer spectrum that exhibits no measurable quadrupole splitting. Two crystallographically distinct [Fe(OH2)6]2+ complexes are identified from inelastic neutron-scattering (INS) experiments conducted between 2 and 15 K. The data are modeled with the ligand-field Hamiltonian, H = lambdaLŝ + betaB(kL + 2ŝ) + Delta(tet){Lz2 - (1/3)L(L + 1)} + Delta(rhom){Lx2 - Ly2}, operating in the ground-term (5)T(2g) (Oh) basis. An excellent reproduction of INS, Mössbauer, HF-EPR, and magnetochemical data are obtained in the 2 and 15 K temperature regimes with the following parameters: lambda = -80 cm(-1); k = 0.8; site A Delta(tet) = 183 cm(-1), Delta(rhom)= 19 cm(-1); site B Delta(tet) = 181 cm(-1), Delta(rhom)= 12 cm(-1). The corresponding zero-field-splitting (ZFS) parameters of the conventional S = 2 spin Hamiltonian are as follows: site A D = 12.02 cm(-)(1), E = 2.123 cm(-1); site B D = 12.15 cm(-1), E = 1.37 cm(-1). A theoretical analysis of the variation of the energies of the low-lying states with respect to displacements along selected normal coordinates of the [Fe(OH2)6]2+, shows the zero-field splitting to be extremely sensitive to small structural perturbations of the complex. The expressions derived are discussed in the context of spin-Hamiltonian parameters reported for the [Fe(OH2)6]2+ cation in different crystalline environments.

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