Scholz, Tanja and Pielnhofer, Florian and Eger, Roland and Lotsch, Bettina (2020) Lanthanide orthothiophosphates revisited: single-crystal X-ray, Raman, and DFT studies of TmPS4 and YbPS4. ZEITSCHRIFT FUR NATURFORSCHUNG SECTION B-A JOURNAL OF CHEMICAL SCIENCES, 75 (1-2). pp. 225-231. ISSN 0932-0776, 1865-7117
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The crystal structures of the lanthanide orthothiophosphates LnPS(4) (Ln = lanthanide) have been extensively investigated in the past. Up to now, however, single crystals of two members of this series - TmPS4 and YbPS4 - have not been available. Here, we report a modified synthesis protocol for TmPS4 and YbPS4 yielding single crystals suitable for X-ray diffraction. Both compounds crystallize in the tetragonal space group I4(1)/acd (no. 142) with 16 formula units per unit cell and adopt the SmPS4 parent structure, like most reported lanthanide orthothiophosphates. The structures contain isolated [PS4](3-) tetrahedra and two crystallographically independent Le cations, which form trigonal-dodecahedral [LnS(8)](13-) polyhedra. The lattice parameters for TmPS4 are a =10.598(2), c=18.877(4) angstrom with V=2120.2(6) angstrom(3), and for YbPS4 a=10.577(2), c =18.827(4)angstrom with V= 2106.2(7) angstrom(3). The DFT-calculated electronic band structures indicate semiconducting behavior and reveal indirect band gaps of 2.1-2.2 eV, consistent with the reddish brown color of YbPS4, but underestimating the band gap of pale-yellow TmPS4. The Raman spectra are dominated by [PS4](3-) vibrations as confirmed by DFT-calculated phonon spectra. DTA measurements reveal remarkably high thermal stability compared to other known orthothiophosphate compounds.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | IONIC-CONDUCTIVITY; THIOPHOSPHATES; COMPOUND; SERIES; electronic band structure; orthothiophosphates; phonon spectra; Raman spectroscopy; rare earth elements; single-crystal X-ray diffraction; thermal stability |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Anorganische Chemie > Chair Prof. Dr. Arno Pfitzner |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 30 Mar 2021 11:48 |
| Last Modified: | 30 Mar 2021 11:48 |
| URI: | https://pred.uni-regensburg.de/id/eprint/45241 |
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