Determination of cation valencies in Cu257Fe119SnS4 by Mössbauer effect and magnetic susceptibility measurements

Eibschütz, M.; Hermon, E.; Shtrikman, S.

doi:10.1016/0022-3697(67)90134-5

Cited by 41 publications

(14 citation statements)

References 9 publications

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“…The slightly smaller value predicted for IS of 0.75 mm/s is possibly due to the absence of some Li in the larger particles, since the maximum amount of Li in the sample is x = 0.86 [10]. This value of the high-spin IS is in very good agreement with IS for FeS (0.77 mm/s) and other sulfides with Fe in octahedral sites [11,12]. The ME spectrum for x = 0.5 is slightly more complex and is different than the spectrum for x = 0 or x = 0.86.…”

supporting

confidence: 71%

Electronic Structure of Iron Substituted Lithium Intercalated TaS₂

Eibschütz¹,

Murphy²,

DiSalvo³

1980

MRS Proc.

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We have used the 57Fe Mossbauer effect to study the electronic spin configuration of Fe substituted in the layer compound LiuTaj.yFeyS 2 (0fxl; 0:y:50.1). The M6ssbauer effect results show that the Fe is localized and in Fe 2 + valence state but the electronic configuration depends on the lithium concentration. At room temperature the isomer shift of Fe 2 + increases from 0.56 mm/s for x = 0 (no Li) to 0.77 mm/s for x = .86 (at y = 0.05). The isomer shift results reflect the changes in the electronic configuration of the host from Ta 4 +(5d') to Ta 3 +(5d 2 ) and an increase in ionicity as the lithium content increases from 0 to 1.

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supporting

confidence: 71%

Electronic Structure of Iron Substituted Lithium Intercalated TaS₂

Eibschütz¹,

Murphy²,

DiSalvo³

1980

MRS Proc.

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“…The values of Fe valence obtained from the measured IS values depend crucially on the validity of the equation of Goodenough & Fatseas (1982). This phenomenon places tennantite (and tetrahedrite) into a group of sulfides in which, owing to the band structure, appreciable differences between formal and effective charges occur for iron, alongside such compounds as Cu 2 FeSnS 4 (Eibschutz et al 1967), thalcusite Tl 2 Cu 3 FeS 4 (Forcher et al 1988), bornite (Townsend et al 1977) and FeCr 2 S 4 (Brossard et al 1980), as opposed to compounds such as stoichiometric chalcopyrite (Greenwood & Whitfield 1968), for which no appreciable deviations from formal charge are claimed. In addition, the electron-transfer phenomenon resulting in broad peaks of "intermediatevalence iron" and the IS values for "Fe 3+ " make the situation in tennantite similar to that in the copper-bearing thiospinels investigated by Riedel et al (1981).…”

Section: Discussionmentioning

confidence: 99%

MOSSBAUER STUDY OF Fe-BEARING SYNTHETIC TENNANTITE

Makovicky¹,

Tippelt²,

Forcher³

et al. 2003

The Canadian Mineralogist

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The valence of iron in synthetic Fe-bearing tennantite was investigated by the Mössbauer method. Tennantite compositions were weighed out in the reference system Cu 12 As 4 S 13-Cu 14 As 4 S 13-Cu 10 Fe 2 As 4 S 13 at the levels with 0.0, 0.5, 1.0, 1.5 and 1.7 Fe apfu. The tennantite compositions obtained were characterized by electron-microprobe analysis and powder-diffraction data. Compositions with a low-level substitution of iron for copper contain Fe 3+. Evidence of divalent iron appears at the level of 1.0 Fe apfu, and for Cu-rich charges, even at 0.5 Fe apfu. It becomes dominant in Cu-rich tennantite at ~1.0 Fe apfu, whereas in Cupoor tennantite, only at ~1.4 Fe apfu. The balance of the iron is in both cases represented by mixed-valence iron, with the values of isomer-shift and quadrupole splitting intermediate between those for Fe 2+ and Fe 3+. Effects of electron delocalization and net charge-transfer in superexchange interactions on the effective valence of iron were modeled using the relation between isomer shift and valence proposed by Goodenough & Fatseas for sulfides.

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“…The field of ......,370 kG at 77 K is smaller than usually found for tetrahedral Fe3+ because of covalency factors. The temperature dependence of the 57Fe quadrupole splitting gives a singletdoublet crystal field splitting of 1700 K (1180 cm-1 ) and a value of i1(0 K) of 2·92 mm S-1 [198]. In the case of CU2FeSnS4, the presence of Sn(IV) was also established by Mossbauer spectroscopy.…”

Section: Fes2 and Related Phasesmentioning

confidence: 85%

“…FeCr2S4 is a normal spinel with Fe 2 + in tetrahedral coordination and a chemical isomer shift of only 0·50 mm S-1 because of increased covalency to iron [198]. Magnetic ordering occurs at 180 K. Above this temperature the resonance shows no quadrupole splitting because of the cubic site symmetry.…”

Section: Fes2 and Related Phasesmentioning

confidence: 99%