Jahn-Teller distortion of Mn<sup>3+</sup>-occupied octahedra in red beryl from Utah indicated by optical spectroscopy

Autor(en)
Jana Fridrichová, Peter Bačík, Andreas Ertl, Manfred Wildner, Július Dekan, Marcel Miglierini
Abstrakt

Red beryl from Utah is chemically homogeneous and contains only Fe < 0.163, Mn < 0.018, and Mg < 0.016 apfu. Channel sites contain only up to Cs 0.011, K 0.009, Rb 0.004, and Na 0.004 apfu. This suggests only very slight tetrahedral (Cs,K,Rb)Li□

-1Be

-1 substitution, octahedral Na(Fe

2+,Mg)□

-1Al

-1 substitution can be excluded. Fe and Mn are trivalent as documented by Mössbauer spectroscopy and optical absorption spectroscopy. Red beryl optimized formula is ∼[(Cs,Rb,K)

0.02

0.98]

Σ1.00

1.00(Al

1.79Fe

3+

0.16Mn

3+

0.02Ti

4+

0.02Mg

0.01)

Σ2.00Be

3(Si

6O

18). Location of Mn

3+ was estimated to the octahedral Al

3+ site, other choices are improbable due to the bond-length requirements. No Mn

3+-induced Jahn-Teller structural distortion was detected due to site symmetry restrictions and small Mn

3+ content. However, optical spectroscopy shows broad band at ∼7190 cm

−1 assigned to the excited level of the spin-allowed pseudo-tetragonal split E ground state of elongated six-fold Mn

3+ coordination. Crystal field calculations indicate that the local Mn

3+ environment complies well with crystal chemical expectations for Jahn-Teller distorted Mn

3+O

6 octahedra.

Organisation(en)
Institut für Mineralogie und Kristallographie
Externe Organisation(en)
Slovak University of Technology in Bratislava, Naturhistorisches Museum Wien (NHM), Univerzita Komenského v Bratislave
Journal
Journal of Molecular Structure
Band
1152
Seiten
79-86
Anzahl der Seiten
8
ISSN
0022-2860
DOI
https://doi.org/10.1016/j.molstruc.2017.09.081
Publikationsdatum
09-2017
Peer-reviewed
Ja
ÖFOS 2012
104026 Spektroskopie, 105116 Mineralogie, 105113 Kristallographie
Schlagwörter
ASJC Scopus Sachgebiete
Analytical Chemistry, Spectroscopy, Inorganic Chemistry, Organic Chemistry
Link zum Portal
https://ucrisportal.univie.ac.at/de/publications/d94289e7-bbfd-46f6-8f24-57dbc95acc84