The crystal chemistry of (Mn 3 + , Fe 3+ )-substituted andalusites (viridines and kanonaite), (Al 1−x−y Mn 3 x + Fe 3 y + ) 2 (OǀSiO 4 ): crystal structure refinements, Mössbauer, and polarized optical absorption spectra
Abstract The crystal chemistry of viridines and kanonaite, (Al 1-x-y Mn 3 x + Fe 3 y + ) 2 (OǀSiO 4 ), has been evaluated with special reference to the behavior of Mn 3+ in this andalusite type structure. Five natural samples (from Ultevis: x = 0.012, y = 0.028; from Yakutia: x = 0.076, y = 0.046; f...
Published in: | Zeitschrift für Kristallographie - Crystalline Materials |
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Language: | English |
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Walter de Gruyter GmbH
1981
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Online Access: | http://dx.doi.org/10.1524/zkri.1981.155.1-2.81 https://www.degruyter.com/document/doi/10.1524/zkri.1981.155.1-2.81/xml https://www.degruyter.com/document/doi/10.1524/zkri.1981.155.1-2.81/pdf |
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crdegruyter:10.1524/zkri.1981.155.1-2.81 2023-05-15T18:45:11+02:00 The crystal chemistry of (Mn 3 + , Fe 3+ )-substituted andalusites (viridines and kanonaite), (Al 1−x−y Mn 3 x + Fe 3 y + ) 2 (OǀSiO 4 ): crystal structure refinements, Mössbauer, and polarized optical absorption spectra Abs-Wurmbach, I. Langer, K. Seifert, F. Tillmanns, E. 1981 http://dx.doi.org/10.1524/zkri.1981.155.1-2.81 https://www.degruyter.com/document/doi/10.1524/zkri.1981.155.1-2.81/xml https://www.degruyter.com/document/doi/10.1524/zkri.1981.155.1-2.81/pdf en eng Walter de Gruyter GmbH Zeitschrift für Kristallographie - Crystalline Materials volume 155, issue 1-2, page 81-113 ISSN 2194-4946 2196-7105 Inorganic Chemistry Condensed Matter Physics General Materials Science journal-article 1981 crdegruyter https://doi.org/10.1524/zkri.1981.155.1-2.81 2022-04-14T05:05:38Z Abstract The crystal chemistry of viridines and kanonaite, (Al 1-x-y Mn 3 x + Fe 3 y + ) 2 (OǀSiO 4 ), has been evaluated with special reference to the behavior of Mn 3+ in this andalusite type structure. Five natural samples (from Ultevis: x = 0.012, y = 0.028; from Yakutia: x = 0.076, y = 0.046; from Tanzania: x = 0.091, y = 0.031; from Darmstadt: x = 0.171, y = 0.048; from Kanona: x = 0.340, y = 0.009) and two synthetic viridines ( P 135: x = 0.173, y = 0.005; P 150: x = 0.22, y = 0) have been studied by means of X-ray powder diffraction, single crystal-structure refinements, 57 Fe y -resonance spectroscopy, and optical absorption microspectroscopy. The structure refinements reveal that the transition metal ions substitute for Al almost exclusively in the distorted octahedral Al(l) site of the andalusite structure type within the entire mixed crystal series. This is independently proven by the Mössbauer results for 57 Fe, which show that only 10 to 15 % of total iron is present in the Al(2) trigonal-bipyramidal site. With increasing substitution, the octahedral ( c/a ) oct ratio increases. This result is corroborated by the increasing energy of the Mn 3+ 5 B 1g → 5 A 1g transition as determined from the optical spectra. The increasing octahedral elongation leads to a tilting of both the Al(2)O 5 trigonal bipyramids and SiO 4 tetrahedra, and to slight changes of several of the Al(2)– O bond distances. These changes, although similar to those observed at high temperatures (Winter and Ghose, 1979), are considerably stronger than those caused by high temperature (e.g.,Δ( c/a ) oct /( c/a ) oct to be extrapolated for x = 0.5 is approximately 0.1 while at 1000°C this relative change is only 0.035]. In the optical spectra, spin-allowed and spin-forbidden transitions of Mn 3 + are identified near 15000 cm- 1 [ 5 B 1g → 5 A 1g ( D )], 18000 cm -1 { 5 B 1g →[ 3 T 1g ( H )]}, 19700cm -1 { 5 B 1g →[ 3 T 1g ( H )]}, 21800cm -1 [ 5 B 1g → 5 B 2g ( D )], 23300cm -1 [ 5 B 1g → 5 E g ( D )] and spin forbidden Fe 3+ transitions near 19700cm -1 { 6 A 1g →[ 4 T 2g ( G )]}, 20800 cm -1 { 6 A 1g →[ 4 T 2g ( G )]}, 22300 cm -1 { 6 A 1g → [ 4 A 1g , 4 E g ]( G )}, 23300cm -1 { 6 A 1g →[ 4 A 1g , 4 E g ]( G )}. The crystal-field parameter 10 Dq for Mn 3+ decreases in the whole series by approximately 10%. However, this effect is compensated by increasing groundstate splitting such that the crystal field stabilazation energy of Mn 3 + is nearly constant, 198 ± 2 kJ/g-atom Mn 3 + , in the whole range of solid solutions, 0.0≤ x ≤ 0.4, which were studied. Article in Journal/Newspaper Yakutia De Gruyter (via Crossref) Tilting ENVELOPE(-54.065,-54.065,49.700,49.700) Ultevis ENVELOPE(18.617,18.617,67.250,67.250) Zeitschrift für Kristallographie - Crystalline Materials 155 1-2 81 113 |
institution |
Open Polar |
collection |
De Gruyter (via Crossref) |
op_collection_id |
crdegruyter |
language |
English |
topic |
Inorganic Chemistry Condensed Matter Physics General Materials Science |
spellingShingle |
Inorganic Chemistry Condensed Matter Physics General Materials Science The crystal chemistry of (Mn 3 + , Fe 3+ )-substituted andalusites (viridines and kanonaite), (Al 1−x−y Mn 3 x + Fe 3 y + ) 2 (OǀSiO 4 ): crystal structure refinements, Mössbauer, and polarized optical absorption spectra |
topic_facet |
Inorganic Chemistry Condensed Matter Physics General Materials Science |
description |
Abstract The crystal chemistry of viridines and kanonaite, (Al 1-x-y Mn 3 x + Fe 3 y + ) 2 (OǀSiO 4 ), has been evaluated with special reference to the behavior of Mn 3+ in this andalusite type structure. Five natural samples (from Ultevis: x = 0.012, y = 0.028; from Yakutia: x = 0.076, y = 0.046; from Tanzania: x = 0.091, y = 0.031; from Darmstadt: x = 0.171, y = 0.048; from Kanona: x = 0.340, y = 0.009) and two synthetic viridines ( P 135: x = 0.173, y = 0.005; P 150: x = 0.22, y = 0) have been studied by means of X-ray powder diffraction, single crystal-structure refinements, 57 Fe y -resonance spectroscopy, and optical absorption microspectroscopy. The structure refinements reveal that the transition metal ions substitute for Al almost exclusively in the distorted octahedral Al(l) site of the andalusite structure type within the entire mixed crystal series. This is independently proven by the Mössbauer results for 57 Fe, which show that only 10 to 15 % of total iron is present in the Al(2) trigonal-bipyramidal site. With increasing substitution, the octahedral ( c/a ) oct ratio increases. This result is corroborated by the increasing energy of the Mn 3+ 5 B 1g → 5 A 1g transition as determined from the optical spectra. The increasing octahedral elongation leads to a tilting of both the Al(2)O 5 trigonal bipyramids and SiO 4 tetrahedra, and to slight changes of several of the Al(2)– O bond distances. These changes, although similar to those observed at high temperatures (Winter and Ghose, 1979), are considerably stronger than those caused by high temperature (e.g.,Δ( c/a ) oct /( c/a ) oct to be extrapolated for x = 0.5 is approximately 0.1 while at 1000°C this relative change is only 0.035]. In the optical spectra, spin-allowed and spin-forbidden transitions of Mn 3 + are identified near 15000 cm- 1 [ 5 B 1g → 5 A 1g ( D )], 18000 cm -1 { 5 B 1g →[ 3 T 1g ( H )]}, 19700cm -1 { 5 B 1g →[ 3 T 1g ( H )]}, 21800cm -1 [ 5 B 1g → 5 B 2g ( D )], 23300cm -1 [ 5 B 1g → 5 E g ( D )] and spin forbidden Fe 3+ transitions near 19700cm -1 { 6 A 1g →[ 4 T 2g ( G )]}, 20800 cm -1 { 6 A 1g →[ 4 T 2g ( G )]}, 22300 cm -1 { 6 A 1g → [ 4 A 1g , 4 E g ]( G )}, 23300cm -1 { 6 A 1g →[ 4 A 1g , 4 E g ]( G )}. The crystal-field parameter 10 Dq for Mn 3+ decreases in the whole series by approximately 10%. However, this effect is compensated by increasing groundstate splitting such that the crystal field stabilazation energy of Mn 3 + is nearly constant, 198 ± 2 kJ/g-atom Mn 3 + , in the whole range of solid solutions, 0.0≤ x ≤ 0.4, which were studied. |
author2 |
Abs-Wurmbach, I. Langer, K. Seifert, F. Tillmanns, E. |
format |
Article in Journal/Newspaper |
title |
The crystal chemistry of (Mn 3 + , Fe 3+ )-substituted andalusites (viridines and kanonaite), (Al 1−x−y Mn 3 x + Fe 3 y + ) 2 (OǀSiO 4 ): crystal structure refinements, Mössbauer, and polarized optical absorption spectra |
title_short |
The crystal chemistry of (Mn 3 + , Fe 3+ )-substituted andalusites (viridines and kanonaite), (Al 1−x−y Mn 3 x + Fe 3 y + ) 2 (OǀSiO 4 ): crystal structure refinements, Mössbauer, and polarized optical absorption spectra |
title_full |
The crystal chemistry of (Mn 3 + , Fe 3+ )-substituted andalusites (viridines and kanonaite), (Al 1−x−y Mn 3 x + Fe 3 y + ) 2 (OǀSiO 4 ): crystal structure refinements, Mössbauer, and polarized optical absorption spectra |
title_fullStr |
The crystal chemistry of (Mn 3 + , Fe 3+ )-substituted andalusites (viridines and kanonaite), (Al 1−x−y Mn 3 x + Fe 3 y + ) 2 (OǀSiO 4 ): crystal structure refinements, Mössbauer, and polarized optical absorption spectra |
title_full_unstemmed |
The crystal chemistry of (Mn 3 + , Fe 3+ )-substituted andalusites (viridines and kanonaite), (Al 1−x−y Mn 3 x + Fe 3 y + ) 2 (OǀSiO 4 ): crystal structure refinements, Mössbauer, and polarized optical absorption spectra |
title_sort |
crystal chemistry of (mn 3 + , fe 3+ )-substituted andalusites (viridines and kanonaite), (al 1−x−y mn 3 x + fe 3 y + ) 2 (oǀsio 4 ): crystal structure refinements, mössbauer, and polarized optical absorption spectra |
publisher |
Walter de Gruyter GmbH |
publishDate |
1981 |
url |
http://dx.doi.org/10.1524/zkri.1981.155.1-2.81 https://www.degruyter.com/document/doi/10.1524/zkri.1981.155.1-2.81/xml https://www.degruyter.com/document/doi/10.1524/zkri.1981.155.1-2.81/pdf |
long_lat |
ENVELOPE(-54.065,-54.065,49.700,49.700) ENVELOPE(18.617,18.617,67.250,67.250) |
geographic |
Tilting Ultevis |
geographic_facet |
Tilting Ultevis |
genre |
Yakutia |
genre_facet |
Yakutia |
op_source |
Zeitschrift für Kristallographie - Crystalline Materials volume 155, issue 1-2, page 81-113 ISSN 2194-4946 2196-7105 |
op_doi |
https://doi.org/10.1524/zkri.1981.155.1-2.81 |
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Zeitschrift für Kristallographie - Crystalline Materials |
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155 |
container_issue |
1-2 |
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81 |
op_container_end_page |
113 |
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