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          Institute: MPI für Festkörperforschung     Collection: FKF Publikationen 2006     Display Documents

ID: 306086.0, MPI für Festkörperforschung / FKF Publikationen 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
Authors:Carver, G.; Dobe, C.; Jensen, T. B.; Tregenna-Piggott, P. L. W.; Janssen, S.; Bill, E.; McIntyre, G. J.; Barra, A. L.
Date of Publication (YYYY-MM-DD):2006
Title of Journal:Inorganic Chemistry
Issue / Number:12
Start Page:4695
End Page:4705
Review Status:Peer-review
Audience:Not Specified
Abstract / Description:Spectroscopic, magnetochemical, and crystallographic data are presented
for CsFe(H2O)(6)PO4, 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) Mossbauer
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)
over cap = lambda(L) over cap(S) over cap + beta B(k (L) over cap +2
(S) over cap)+Delta(tet){(L) over cap (2)(z)-(1/3)L(L+1)} + Delta(rhom)
{(L) over cap (2)(x)-(L) over cap (2)(y)}, operating in the ground-term
T-5(2g) (O-h) basis. An excellent reproduction of INS, Mossbauer,
HF-EPR, and magnetochemical data are obtained in the 2 and 15 K
temperature regimes with the following parameters: I) - 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.
External Publication Status:published
Document Type:Article
Communicated by:N. N.
Affiliations:MPI für Festkörperforschung
External Affiliations:Univ Bern, Dept Chem & Biochem, CH-3012 Bern, Switzerland.
; Paul Scherrer Inst, CH-5232 Villigen, Switzerland.
; ETH, Neutron Scattering Lab, CH-5232 Villigen, Switzerland.
; Max Planck Inst Bioanorgan Chem, D-45470 Mulheim, Germany.
; Inst Max Von Laue Paul Langevin, F-38042 Grenoble 9, France.
; MPI, CNRS, High Field Magnet Lab, F-38042 Grenoble, France.
Identifiers:ISI:000238029400018 [ID No:1]
ISSN:0020-1669 [ID No:2]
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