Anionic ordering in Pb2Ti4O9F2 revisited by nuclear magnetic resonance and density functional theory
A combination of 19F magic angle spinning (MAS) nuclear magnetic resonance (NMR) and density functional theory (DFT) were used to study the ordering of F atoms in Pb2Ti4O9F2. This analysis revealed that F atoms predominantly occupy two of the six available inequivalent sites in a ratio of 73 : 27. D...
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| Veröffentlicht in: | Dalton transactions : an international journal of inorganic chemistry 2022-10, Vol.51 (40), p.15361-15369 |
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| container_title | Dalton transactions : an international journal of inorganic chemistry |
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| creator | Oka, Kengo Ichibha, Tom Kato, Daichi Noda, Yasuto Tominaga, Yusuke Yamada, Kosei Iwasaki, Mitsunobu Noma, Naoki Hongo, Kenta Maezono, Ryo Reboredo, Fernando A |
| description | A combination of 19F magic angle spinning (MAS) nuclear magnetic resonance (NMR) and density functional theory (DFT) were used to study the ordering of F atoms in Pb2Ti4O9F2. This analysis revealed that F atoms predominantly occupy two of the six available inequivalent sites in a ratio of 73 : 27. DFT-based calculations explained the preference of F occupation on these sites and quantitatively reproduced the experimental occupation ratio, independent of the choice of functional. We concluded that the Pb atom's 6s2 lone pair may play a role (∼0.1 eV per f.u.) in determining the majority and minority F occupation sites with partial density of states and crystal orbital Hamiltonian population analyses applied to the DFT wave functions. |
| doi_str_mv | 10.1039/d2dt00839d |
| format | Article |
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This analysis revealed that F atoms predominantly occupy two of the six available inequivalent sites in a ratio of 73 : 27. DFT-based calculations explained the preference of F occupation on these sites and quantitatively reproduced the experimental occupation ratio, independent of the choice of functional. 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| source | Royal Society Of Chemistry Journals 2008-; Alma/SFX Local Collection |
| subjects | Density functional theory INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY NMR Nuclear magnetic resonance Wave functions |
| title | Anionic ordering in Pb2Ti4O9F2 revisited by nuclear magnetic resonance and density functional theory |
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