Anionic ordering in Pb2Ti4O9F2 revisited by nuclear magnetic resonance and density functional theory

Kengo Oka; Tom Ichibha; Daichi Kato; Yasuto Noda; Yusuke Tominaga; Kosei Yamada; Mitsunobu Iwasaki; Naoki Noma; Kenta Hongo; Ryo Maezono; Fernando A. Reboredo

doi:10.1039/D2DT00839D

Anionic ordering in Pb₂Ti₄O₉F₂ revisited by nuclear magnetic resonance and density functional theory†‡

Kengo Oka,

§*^a Tom Ichibha,

§*^b Daichi Kato,

^c Yasuto Noda,^d Yusuke Tominaga,^d Kosei Yamada,^a Mitsunobu Iwasaki,^a Naoki Noma,^e Kenta Hongo,

^f Ryo Maezono

^g and Fernando A. Reboredo^b

Author affiliations

* Corresponding authors

^a Department of Applied Chemistry, Faculty of Science and Engineering, Kindai University, Higashiosaka, Osaka 577-8502, Japan
E-mail: koka@apch.kindai.ac.jp

^b Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831, USA
E-mail: ichibha@icloud.com

^c Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Kyoto 615-8510, Japan

^d Division of Chemistry, Graduate School of Science, Kyoto University, 606-8502 Kyoto, Japan

^e Joint Research Center, Kindai University, Higashiosaka, Osaka 577-8502, Japan

^f Research Center for Advanced Computing Infrastructure, JAIST, Asahidai 1-1, Nomi, Ishikawa 923-1292, Japan

^g School of Information Science, JAIST, Asahidai 1-1, Nomi, Ishikawa 923-1292, Japan

Abstract

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.

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Anionic ordering in Pb₂Ti₄O₉F₂ revisited by nuclear magnetic resonance and density functional theory†‡

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Anionic ordering in Pb₂Ti₄O₉F₂ revisited by nuclear magnetic resonance and density functional theory

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