Abstract
The structural relations of (and between) late transition metal monoxides, MO, and monosulfates, MSO4, are analyzed. We show that all of these late transition metal oxides, as well as 4d and 5d metal sulfates, crystallize in distorted rock salt lattices and argue that the distortions are driven by collective first- and/or second order Jahn-Teller effects. The collective Jahn-Teller deformations lead either to tetragonal contraction or (seldom) elongation of the rock salt lattice. On the basis of the rock salt representation of the oxides and sulfates, we show that PdO, CuO, and AgO are metrically related and that the 4d and 5d metal sulfates are close to isostructural with their oxides. These observations guide us towards as yet unknown AuO and PtSO4, for which we predict crystal structures from electronic structure calculations. The structural relations of (and between) late transition metal monoxides, MO, and monosulfates, MSO4, are analyzed. We show that all of these late transition metal oxides, as well as 4d and 5d metal sulfates, crystallize in distorted rock salt lattices and argue that the distortions are driven by collective first- and/or second order Jahn-Teller effects, as quantified by the c′/a′ ratio. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
| Original language | English (US) |
|---|---|
| Pages (from-to) | 5094-5102 |
| Number of pages | 9 |
| Journal | European Journal of Inorganic Chemistry |
| Volume | 2013 |
| Issue number | 29 |
| DOIs | |
| State | Published - Aug 21 2013 |
| Externally published | Yes |
Bibliographical note
KAUST Repository Item: Exported on 2020-10-01Acknowledged KAUST grant number(s): k128
Acknowledgements: W. G. acknowledges support from the project "AgCENT: New Unique Magnetic and Electronic Materials based on Compounds of Divalent Silver" from the Polish National Science Centre (NCN). DFT calculations were performed at ICM supercomputers within grant G29-3. A. H. and R. H. are grateful for support from EFree, an Energy Frontier Research Center funded by the U.S. Department of Energy (grant number DESC0001057 at Cornell) and from the U.S. National Science Foundation (NSF) (grant number CHE-0910623). Computational resources provided by the Cornell NanoScale Facility (supported by the U.S. National Science Foundation (NSF) through grant ECS-0335765), the XSEDE network (provided by the National Center for Supercomputer Applications through grant TG-DMR060055N), and the KAUST Supercomputing Laboratory (project ID k128) are gratefully acknowledged. M. D. and W. G. are grateful to Dr. Piotr Leszczyski for valuable discussions.
This publication acknowledges KAUST support, but has no KAUST affiliated authors.