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| 100 | 1 | _ | |a Bykov, Maxim |0 P:(DE-HGF)0 |b 0 |e Corresponding author |
| 245 | _ | _ | |a High-Pressure Phase Transformations in $\mathrm{TiPO_{4}}$: A Route to Pentacoordinated Phosphorus |
| 260 | _ | _ | |a Weinheim |c 2016 |b Wiley-VCH |
| 336 | 7 | _ | |a article |2 DRIVER |
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| 500 | _ | _ | |a (c) Wiley-VCH Verlag GmbH & Co. Post referee full text in progress (embargo 1 year from 31 OCT 2016). |
| 520 | _ | _ | |a Titanium(III) phosphate, TiPO$_4$ , is a typical example of an oxyphosphorus compound containing covalent P−O bonds. Single-crystal X-ray diffraction studies of TiPO$_4$ reveal complex and unexpected structural and chemical behavior as a function of pressure at room temperature. A series of phase transitions lead to the high-pressure phase V, which is stable above 46 GPa and features an unusual oxygen coordination of the phosphorus atoms. TiPO$_4$-V is the first inorganic phosphorus-containing compound that exhibits fivefold coordination with oxygen. Up to the highest studied pressure of 56 GPa, TiPO$_4$-V coexists with TiPO$_4$-IV, which is less dense and might be kinetically stabilized. Above a pressure of about 6 GPa, TiPO$_4$-II is found to be an incommensurately modulated phase whereas a lock-in transition at about 7 GPa leads to TiPO$_4$-III with a fourfold superstructure compared to the structure of TiPO$_4$-I at ambient conditions. TiPO$_4$-II and TiPO$_4$-III are similar to the corresponding low-temperature incommensurate and commensurate magnetic phases and reflect the strong pressure dependence of the spin-Peierls interactions. |
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| 700 | 1 | _ | |a van Smaalen, Sander |0 P:(DE-H253)PIP1008136 |b 7 |
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