Materials Research Bulletin, Vol. 33, No. 12, pp.

18211833, 1998 Copyright 1999 Elsevier Science Ltd Printed in the USA. All rights reserved 0025-5408/98 $19.00 .00

PII S0025-5408(98)00184-6

COVALENCY OF Fe3O2 BONDS AND MAGNETIC STRUCTURE IN MIXED OXIDES ims M. Lenglet*1, F. Hochu1, and Z. S a2 L.A.S.T.S.M., Universite de Rouen, IUT, 76821 Mont Saint Aignan Cedex, France 2 ASCR, Institute of Physics, Cukrovarnicka 10, 162 53 Praha 6, Czech Republic (Communicated by B. Raveau) (Received April 10, 1998; Accepted April 10, 1998)

ABSTRACT Optical absorption and the Faraday rotation spectra of iron(III) in ferrimagnetic oxides may be interpreted using 3d crystal eld and the pair excitation processes. Band assignments and ligandeld parameters are in agreement with the results of SCF-X-SW molecular orbital calculations of (FeO4)5 and (FeO6)9 clusters. The pair excitation processes are strongly inuenced by the nature and strength of the superexchange interactions. The presence of the ferrimagnetism in ferrites and garnets induces greater covalency effects of the Fe3O2 bonds. The nephelauxetic ratios 35 of iron(III) in hematite, ferrites, and garnets show that the greater covalency of the Fe3O2 chemical bonds in these oxides is related to the magnetic structure. 1999 Elsevier
Science Ltd

KEYWORDS: A. oxides, D. magnetic properties, D. optical properties INTRODUCTION A common point of view is absent regarding the origin of the iron(III) transitions capable of explaining principal optical and magneto-optical effects in ferrites and garnets. The optical absorption in the range of 12 eV is mainly due to crystal eld transitions of octahedral Fe3. The increased absorption at higher energies (2 4 eV) has been explained by several processes:

*To whom correspondence should be addressed. 1821

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3d crystal eld (or ligand eld) (CF) transitions to higher states of octahedral and/or tetrahedral Fe3 [1]. 2. Pair transitions (PT) where the double exciton processes involve exchange-coupled pairs of Fe3 ions [1]. 3. 3d intra-sublattice charge transfer (ISCT) transitions such as 2 Fe3 3 Fe2 Fe4 [2]. 4. 3dn 3 3dn1 4s orbital promotion transitions [3]. A special purpose of the present work was to reinvestigate the optical and magneto-optical spectra of Fe3 as inuenced by the concentration of Fe3 ions and magnetic structure. Substitution of diamagnetic ion for Fe3 lowers the optical absorption and weakens the exchange interactions. It induces strong changes in the magnetic properties [4 6] and reveals the individual electronic transitions. Based on the ligand eld theory and the results of SCF-X-SW molecular orbital calculations, detailed band assignments of Fe3 electronic spectra in oxides are given. The latter interpretation is extended also to the magneto-optical Faraday rotation spectra. EXPERIMENTAL Diffuse reectance of polycrystalline samples were obtained using a Perkin-Elmer Lambda 9 spectrophotometer equipped with an integrating sphere accessory coated with BaSO4. For an easier comparison in the near-infrared and visible region, the spectra of iron-rich oxides were converted to the KubelkaMunk remission function dened by F(R) (1 R) 2 k 1R s

1.

where R is the reectance and k the absorption coefcient. Assuming that the scattering coefcient s has a small variation with the wavelength over the range of interest, the shapes of the remission function and absorption spectra are identical. YIG lms were prepared by a liquid phase epitaxy on the 111 oriented gadolinium gallium garnet substrates. The measurements of the Faraday rotation F in the visible and near infrared regions (500 2500 nm) were performed by the conventional method as described elsewhere [79]. RESULTS AND DISCUSSION Spectra of Octahedral Fe3 in Reference Compounds. The most extensively investigated octahedral Fe3 system in the past and undeniably the most reliable of any octahedral Fe3 system is the Fe3 substitution in Al2O3 [1,10,11]. The complexity of octahedral Fe3 spectra in oxides and minerals is due to the effect of magnetic coupling between the next nearest Fe3 neighbors on the ligand eld transitions. All the transitions from the 6A1(6S) ground state to the excited ligand eld states are, in principle, both spin and parity forbidden and their intensities should be very small. In the spectra of iron oxides, however, the nominally spin forbidden Fe3 ligand eld transitions are found to be quite intense. The apparent relaxation of the spin selection rule results from the magnetic coupling of the nearest neighbor 3d5 cations [1115]. If two Fe3 cations are strongly coupled, one must consider the spectroscopic rules for the Fe3Fe3 pairs instead of the individual Fe3 centers. Another

Vol. 33, No. 12

TABLE 1 Energies and Assignments of Bands Observed in Fe3 Systems

System
6

Observed electronic CF transition energies (103 cm1) A1g 3

4

Ligand eld parameters PT2 29.8 29.5 28.5 10Dq 15.27 14.9 15.6 B 0.65 0.63 0.60 C 3.16 3.14 3.1 Ref. IRON OXYGEN BONDS 10,11 1 17

T1g

T2g

PT1 18.3 17

Eg, 4A1g 22.27 22 21.5

T2g

Eg

Al2O3:Fe3 ZnFe0.2Ga1.8O4

9.45 9.55 8.4

14.35 14.4 12.9

25.51 25.5

26.8 26.4 25.7

PT (pair transitions) PT1: 2 6A1g 3 2 4T1g, PT2: 2 6A1g 3 4Eg, 4A1g 4T1g

TABLE 2 3 Energies of the Charge Transfer Transition 6t Systems lu 3 2t2g in Octahedral Fe

System Energy (103 cm1) Reference
a

MgO:Fe3 35.5 18

Al2O3:Fe3 38.6 19

ZnFe0.1Ga1.9O4a 34.5 17

The 4T1(4P) transition located near 33000 cm1 is obscured by the LMCT transition.

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FIG. 1 KubelkaMunk remission spectra of octahedral iron(III) in the ZnFe2xGaxO4 system (1: x 0; 2: x 1; and 3: x 1.5). phenomenon, resulting from the magnetic coupling of adjacent Fe3 cations, is the presence of new absorption features corresponding to the excitation of Fe3 pairs. These features occur at energies given approximately by the sum of two single ion Fe3 ligand eld transitions and are often referred to as double exciton processes [1,16]. The compounds chosen to illustrate the interpretation of ligand eld spectra in oxidic spinels with BB antiferromagnetic coupling belong to the ZnGa2xFexO4 system. The band assignment proposed for diluted compounds is in agreement with that of Ferguson and Fielding [1] for Fe3 in Al2O3 (see Table 1). One important feature of our data is a concentration dependence of the room temperature band absorbance: the intensity of the 6A1g 3 4T1g transition is proportional to the number of Fe3 ions present while the intensities of the 2 6A1g 3 2 4T1g and 6A1g 3 4A1g,4Eg transitions (respectively at 17000 and 21300 cm1) are roughly proportional to the square of the iron(III) concentration. In iron-rich oxides, the exchange-enhanced bands dominate the optical spectrum. The lowest energy ligand-to-metal-charge transfer (LMCT) transition, 3 6t systems is observed at about 35000 cm1 (see Table 2). lu 3 2t2g in octahedral Fe AB Antiferromagnetic Interactions and Fe3 Optical Spectra in Spinels and Garnets. For an easier comparison, the optical absorption spectra of zinc ferrigallates (Fig. 1) and magnesium ferrigallates (Fig. 2) were converted to the KubelkaMunk remission function. The intensities of the 6A1g 3 4T1g and 6A1 3 4T1(4G) crystal eld transitions are reduced with increasing gallium content (Table 3). The experimental ratios I19000/[Fe3]2 octa for spinels and 500/[Fe3]2 octa for garnets show that the absorption observed in the range

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FIG. 2 KubelkaMunk remission spectra (at room temperature) of ferrimagnetic (1: x 0; 2: x 0.4; and 3: x 0.6) and paramagnetic (4: x 1 and 5: x 1.5) compounds of the MgFe2xGaxO4 system. 18000 20000 cm1 (i.e., 550 500 nm) is mainly due to the 2 6A1g 3 2 4T1g transition. Consequently, the strong absorption edge common to orthoferrites ([20], -Fe2O3 [21], and ferrimagnetic MFe2O4 (M 0.5Li 0.5Fe3, Mg2, Ni2) near 2 eV may be assigned to a pair transition, i.e. the biexciton process. The shift of the absorption edge to higher energies with increasing x values may be explained by the decreasing of the biexciton band and that of the ligand eld transition 6A1 3 4E,4A1 and 6A1g 3 4Eg,4A1g in the range 21000 22000 cm1 with gallium substitution. It is worth noting that Wood and Remeika [22] found that the absorbance of the octahedral and tetrahedral 4T1(4G) band in Y3(FexGa1x)5O12 varied as x1.8 over the range 0.03 x 1. An examination of the temperature and concentration dependence of the optical absorption spectra of Fe3 in Al2O3 at the highest concentration investigated indicates that the exchange interaction plays an important role in the intensity of the 4Eg,4A1g and 4Eg bands [11]. On increasing x the spectrum of ferrimagnetic compounds (Fig. 2) is shifted towards longer wavelengths. In particular the shift of the octahedral 6A1g 3 4T1g band is about 100 nm for magnesium substituted ferrites (Fig. 2). The optical spectra of spinels having low Curie temperature in the Li0.5Fe2.5xGaxO4 [6] or Mg Fe2xGaxO4 systems are characterized by a clear display of transitions located near 21500 and 24500 cm1 (the latter is probably a pair transition). The paramagnetic compounds at room temperature present a spectrum similar to that of zinc ferrites (curves 4 and 5, Fig. 2) for octahedral iron(III): a strong intensication of the 2 6A1g 3 4Eg,4A1g 4T1g transition near 29000 cm1 is observed.

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TABLE 3 Correlation Between the Iron Concentrations of Tetrahedral (Td) and Octahedral (Oh) Sites and the Optical and Magnetic Data in Spinels and Garnets
Iron concentrations System x Fe
3

Magnetic data m (B) Ref. SPINELS I10000/Fe

3 octa

Optical measurements
I16000/Fe3 tetra 2 I19000/[Fe3 octa]

(Td) Fe

(Oh) (K)

Ref.

MgFe2xGaxO4

Li0.5Fe2.5xGaxO4

0 0.4 0.6 1 1.5 0 0.5 1 1.25 1.5

0.93 0.61 0.50 0.40 1 0.65 0.46 0.42 0.38

1.07 0.99 0.90 0.60 1.5 1.35 1.04 0.83 0.62

648 508 413 208 893 673 448 343 235

0.72 1.89 2.00 1.05 2.60 2.95 2.90 2.13 1.20

32

1.5 0.32 0.36 0.27 0.87 0.33 0.20

6.5 2.3 1 6 4.5 2.5 2

33

8.1 7.3 7.4 6 7.5 4.1 4.4 4.6 5.8 5.2

a 600/Fe3 tetra

this study M. LENGLET et al.

GARNETS a 920/Fe3 octa Y3Fe5xGaxO12 0 1.15 1.46 1.93 2.45 2.95 3 1.95 1.66 1.28 1.05 0.80 2 1.90 1.88 1.79 1.5 1.25 550 400 350 260 150 82.5 58 50 42 33 24

a 700/Fe3 octa

2 500/[Fe3 octa]

29

173 124 110 73 37

300 350

570 625 700 650

30 30 29 29 Vol. 33, No. 12

200

Data issued from ref. 29. I10000: intensity at 10000 cm1 (6A1g 3 4T1g) measured on the reectance spectrum. 920: optical absorption coefcient at 920 nm. I19000 and 500 are relative to the 2 6A1g 3 2 4T1g pair transition.
a

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TABLE 4 Racah Parameters Data for Iron(III) in Garnets

Compounds Y3Fe0.09Ga4.91O12 Y3Fe5O12 Y3Fe5O12 dFeO (nm) Btetra (cm1) 744 705 900 dFeO (nm) Bocta (cm1) 530 530 700 Ref. 30 30 22

0.187

0.202

Crystal-Field Analysis of Optical and Magneto-Optical Spectra. The optical and magneto-optical properties of ferrites [2,4,6,8,9,20,2328] and garnets [3,4,5,7,2224,29 31] are always the subject of discussion. In this paper, it is shown that a crystal-eld analysis may explain also the magneto-optical properties of these mixed oxides. Nevertheless, some results of previous studies (band assignments and crystal-eld ts) must be revised. For example, the Racah parameters calculated for iron(III) in garnets are inconsistent with lengths and covalencies of Fe3 oxygen bonds (see Table 4). Consequently, the optical absorption spectra of dilute iron ferrites ZnGa2O4:Fe3 and Li0.5Ga2.5O4:Fe3 have been reinvestigated (Fig. 3) and compared to those of Y3Ga5O12: Fe3. The band assignment and ligand eld parameters are given in Table 5. The ligand eld parameters are calculated using the TanabeSugano expressions for the ligand eld state energies 4T1(4G), 4T2(4G) and 4E,4A1(4G) and the values obtained can be used in order to determine the energies of remaining transitions. In some cases the Racah parameters are directly calculated using the energies of the crystal eldindependent levels 4E(4D) 4 4 E, A1(4G). Detailed band assignments of electronic spectra of iron(III) in ferrimagnetic spinels and garnets are given in Table 6. This interpretation may be extended to Faraday rotation spectra (Fig. 4). The similarity between ferrites and YIG is not surprising due to the presence of identical Fe3 sites. However, in addition to this, the tetrahedral and octahedral Fe3 sites in both compounds are characterized by approximately the same

FIG. 3 Absorption spectra (in absorbance) of iron dilute compounds (1: ZnFe0.1Ga1.9O4; 2: L0.5Fe0.05Ga2.45O4).

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TABLE 5 Energies (in 103 cm1) and Assignments of Bands Observed in Iron(III) Systems
Ligand eld parameters (103 cm1)
4

System
6

Fe3 octahedral A1g 3

3 4

T1g

T2g

Eg, 4A1g

T2g

Eg

10Dq 15.6 15.5 13.65

B 0.60 0.56 0.48

C 3.10 3.28 3.26

ZnGa2O4:Fe

Li0.5Ga2.5O4:Fe3 Y3Ga5O12:Fe3a

8.4 (8.4) 9.2 (9.2) 10.3 (10.25)

12.9 (12.92) 13.4 (13.45) 13.8 (13.9)

21.5 (21.5) 22 (22) 21.05 (21.05)

(23.64) 22.73 (22.54)

25.7 (25.7) 25.9 (25.9) 24.38 (24.38)

Fe3 tetrahedral
6

Ligand eld parameters (103 cm1)

4

A1 3

T1

T2

E, 4A1

T2

10Dq 8 7.73

B 0.47 0.48

C 3.28 3.16

Li0.5Ga2.5O4:Fe3 Y3Ga5O12:Fe3 a

15.6 (15.71) 15.4 (15.3)

19.05 (19.1) 18.7 (18.8)

21.1 (21.1) 20.6 (20.6)

22.43 (22.51) 22.04

24.39 (24.39) 23.95 (23.95)

Values in parentheses are the predicted transition energies, based on the Tanabe-Sugano expressions. a Experimental data of Scott et al. [30]. The band assignments proposed in this paper are similar to those given in ref. 30, except for the 4E and 4Eg levels (bands of higher energy may arise from excitation of double excitons). The pair transitions are not mentioned.

point symmetry and size of the oxygen polyhedra. Secondly, the exchange interactions Fe3(octa)O2Fe3(tetra) occur at nearly the same angles and distances, giving rise to two magnetic sublattices (see Table 7). From the above-mentioned data, the following conclusions may be drawn:
Y

Optical absorption and Faraday rotation spectra of iron(III) in ferrimagnetic oxides may be interpreted using the ligand eld theory. The ligand eld parameters are in agreement with the results of SCF-X-SW molecular orbital calculations [39] (see Table 8). The ligand eld transitions unaffected by a double exciton process are strongly enhanced by the AB interactions. The overlapping contributions of many transitions make an assignment of spectra always disputable and prevent the calculation of Fe3 tetrahedral ligand eld parameters: the band at 19000 cm1 is unambiguously a composite of the 6A1 3 4T2 and 2 6A1g 3 2 4T1g transitions and that in the range 21000 21500 cm1 is probably relative to the 6A1 3 4 4 E, A1 transition (the corresponding transition of octahedral Fe3 is not observed on the diffuse reectance spectra). AB interactions induce a stronger enhancement of the 2 6A1g 3 2 4T1g pair transition than BB interactions.

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TABLE 6 Crystal Field Analysis of Absorption and Faraday Rotation Spectra in Ferrites and Garnets
Energy in eV of the observed bands Proposed assignment
6 6

-Fe2O3 1.325 1.86 1.93 2.43 2.25 2.44 2.645 2.85 21 (a) 26 24 2.36 2.60 2.40 2.67 1.29 1.84

Li0.5Fe2.5O4 1.31 1.80 1.995 2.02 2.28 2.355 2.63 1.78 2.03 2.35

MgFe2O4 1.28 1.76 2.04 2.29 2.39 2.65 2.53 2.61 2.85 1.26 1.375 1.77 2.03 1.34 1.81 2.04 2.48 2.57 2.65 2.79 (a) 2.46 2.56 2.66 2.79 3

Y3Fe5O12 IRON OXYGEN BONDS 1.36 1.80 2.05 2.48 2.56 2.66 2.79 2.88 30 1.35a 1.75
a

A1g 3 4T1g A1g 3 T2g

4

1.74 2.06 2.33

6 6

A1 3 4T1

2.07a 2.34a 2.60 2.85 3 2.56 2.66 2.79 2.88 30

A1 3 4T2 and pair transistion 1 6 A1 3 4E, 4A1 6 A1g 3 4Eg, 4A1g 6 A1g 3 4T2g and pair transition 2 Reference

2.60

1.29 1.63 1.84 1.98 2.10 2.29 2.46 2.57 2.65 2.86 31

24

(a)

22

26

a Average value. (a) This study. 1.325, 1.29: optical absorption. 1.35, 1.29: Faraday rotation. Pair transition 1: 2 6A1g 3 2 4T1g. Pair transition 2: 2 6A1g 3 4T1g 4T2g.

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FIG. 4 Diffuse reectance spectra of Li0.5Fe2.5O4 (1) and Y3Fe5O12 (2), and Faraday rotation spectrum of Y3Fe5O12 (3).

TABLE 7 Fe3O2 Distances in Ferrites and Garnets (in nm)

Fe3tetrahedral -Fe2O3 0.186 (2) 0.188 0.192 (0.188) Li0.5Fe2.5O4 0.188 (3) 0.192 (0.189) CoFe2O4 0.190 NiFe2O4 0.188 ZnFe2O4 Y3Fe5O12 0.187 Fe3octahedral 0.198 (2) 0.204(2) 0.198 (4) 0.206(2) 0.199 0.199 0.199 0.202 0.208(2) (0.203) (0.201) Ref. 34 35 36 37 37 38

TABLE 8 Ligand Field Parameters of (FeO6)9 and Fe(O4)5 Clusters

Calculated Cluster (FeO6)9 (FeO4)5 10 Dq 1515.8 8.23 B 0.640.73 0.580.62 LMCT 38.1 40.4 10 Dq 1315.5 7.58 Experimental B 0.600.65 0.530.57 LMCT 34.538.6 40

The values for Racah parameter B and the ligand-to-metal-charge-transfer (LMCT) transition energies are given in 103 cm1.

Vol. 33, No. 12

TABLE 9 Racah Parameters for Fe3 in Silicates and Oxides

Fe3 octahedral B Al2O3:Fe3 ZnFexGa2xO4 ZnFe2O4a -FeOOHa -FeOOHa -FeOOOHa -FeOOOHa silicates -Fe2O3a
a b

Fe3 tetrahedral Ref. 1, 10, 11 17 this study this study 21 this study 21 46 40 LiAlO2:Fe3 orthoclase orthoclase phlogopite B 570 560 550 530 Ref. 41 42 43 44

Fe3 in both coordinations IRON OXYGEN BONDS Btetra Li0.5FexGa2.5xO4 Y3FexGa5xO12 Li0.5Fe2.5O4b MgFe2O4b Y3Fe5O12b 510 470 475 Bocta 560 480 520 520 500 Ref. this this this this this 45 study study study study study

640 600 600 575 590 625 610 560670 520

N: ZnFe2O4, 9 K; FeOOH, 393 K; -FeOOOH, 73 K; Fe2O3, 958 K. C: Li0.5Fe2.5O4, 873 K; MgFe2O4, 648 K; Y3Fe5O12, 553 K.

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TABLE 10 Comparison of Effective Charges Deduced from OES and Other Methods
MnO Ionicity Effective charge: Experimental From OESa [52]
a

FeF3 65% [49]

Ca3Fe2Si3O12 (andradite)

-FeOOH

-Fe2O3 44% [39], 57% [49]

70% [51] 1.3 [50] 1.5

1.75

1.7 [49] 1.35

1.6 [49] 1.351.4

1.4 [48], 1.9 [50] 1.2

OES orbital expansion spectroscopy.

The pair excitation processes depend on the nature and strength of the superexchange interactions.

Racah Parameters and Fe3Oxygen Bond Covalency. The Racah parameters reported for Fe3 in tetrahedral and/or octahedral environments of oxides or silicates (Table 9) may be discussed in terms of metal oxygen covalency. Our Fe3 B values in conjunction with the values of the literature indicate the following order of Fe3 covalency: Fe3 octahedral in dilute phases (silicates and oxides) and condensed phases containing Fe3 ions in octahedral sites alone Fe3 tetrahedral in dilute phases oxides with Ne el ordering (ferrites and garnets) or antiferromagnetic coupling across shared faces (Fe2O3). The 35 ratios (B35 compound/B35 free ion) of the isoelectronic 3d5 Mn2 and Fe3 in the following sequences reveal that the greater covalency of the iron oxygen bond in hematite and ferrimagnetic oxides is mainly due to the magnetic structures of these compounds: MnF2, 0.73; silicates, 0.70; Mn2SiO4, 0.67; MnO, 0.63 3 FeF3 , 0.56; silicates, 0.53; Fe2O3, MFe2O4, and YIG, 0.43 0.45 6 , 0.65; Al2O3:Fe The qualititative relationship between B and the composition of tetrahedral sites observed by Manning [46] for garnets may be explained by the inductive effect of the competing bond [47]. The effective charges deduced from optical measurements are in good agreement with those experimentally determined (infrared spectroscopy [48], X-ray emission [49], and Auger spectrometry [50] or calculated [51,39] (see Table 10). REFERENCES
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