% IMPORTANT: The following is UTF-8 encoded. This means that in the presence % of non-ASCII characters, it will not work with BibTeX 0.99 or older. % Instead, you should use an up-to-date BibTeX implementation like “bibtex8” or % “biber”. @ARTICLE{Friedrich:291398, author = {Friedrich, Alexandra and Winkler, Björn and Morgenroth, Wolfgang and Perlov, Alexander and Milman, Victor}, title = {{P}ressure-induced spin collapse of octahedrally coordinated $\mathrm{{M}n^{3+}}$ in the tetragonal hydrogarnet henritermierite $\mathrm{{C}a_{3}{M}n_{2}[{S}i{O}_{4}]_{2}[{O}_{4}{H}_{4}]}$}, journal = {Physical review / B}, volume = {92}, number = {1}, issn = {1098-0121}, address = {College Park, Md.}, publisher = {APS}, reportid = {PUBDB-2015-05370}, pages = {014117}, year = {2015}, abstract = {The high-pressure behavior of natural henritermierite garnet with close to end-member composition Ca$_{3}$Mn$_{2}$[SiO$_{4}$]$_{2}$[O$_{4}$H$_{4}$] was studied at pressures up to 80 GPa using single-crystal synchrotron x-ray diffraction, Raman spectroscopy, and quantum-mechanical calculations based on density functional theory. An isosymmetric phase transition was observed in the pressure range between 55 and 70 GPa, which is associated with a gradual high-spin to low-spin electronic transition in Mn$^{3+}$ and a pronounced reduction of the Jahn-Teller distortion of the Mn$^{3+}$O$_{4}$(OH)$_{2}$ octahedra. In the high-pressure phase the Jahn-Teller distortion is totally suppressed and the Mn$^{3+}$ is in a low-spin configuration. Experimental structural data before and after the phase transition are in excellent agreement with the theoretically predicted structural compression of the high-spin and low-spin phases, respectively. While the overall unit-cell volume is reduced by about 1.5\% across the phase transition, a collapse of about 4–5\% of the MnO6 octahedral volume is observed. The high-spin phase shows a bulk modulus B = 101(1) GPa and its pressure derivative B'= 4.5(1). The bulk moduli of the coordination polyhedra are B$_{MnO6}$ = 178(2) GPa, B$_{Ca1O8}$ = 101.2(5) GPa, B$_{Ca2O8}$ = 88.4(8) GPa, B$_{SiO4}$= 337(5) GPa, and B$_{O4H4}$ = 29(1) GPa for the high-spin phase. Mode Gr¨uneisen parameters range between 0.34 and 0.94. The computed spin-pairing energy is ≈3.6 eV at 0 GPa.}, cin = {DOOR}, ddc = {530}, cid = {I:(DE-H253)HAS-User-20120731}, pnm = {6G3 - PETRA III (POF3-622) / FS-Proposal: I-20130285 (I-20130285) / FS-Proposal: I-20140699 (I-20140699)}, pid = {G:(DE-HGF)POF3-6G3 / G:(DE-H253)I-20130285 / G:(DE-H253)I-20140699}, experiment = {EXP:(DE-H253)P-P02.2-20150101}, typ = {PUB:(DE-HGF)16}, UT = {WOS:000358841400001}, doi = {10.1103/PhysRevB.92.014117}, url = {https://bib-pubdb1.desy.de/record/291398}, }