Anionic ordering in Pb2Ti4O9F2revisited 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 Pb₂Ti₄O₉F₂revisited 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

Materials Theory

Research output: Contribution to journal › Article › peer-review

1 Scopus citations

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.

Original language	English
Pages (from-to)	15361-15369
Number of pages	9
Journal	Dalton Transactions
Volume	51
Issue number	40
DOIs	https://doi.org/10.1039/d2dt00839d
State	Published - Nov 28 2022

Funding

The authors acknowledge Erica Heinrich for valuable help with manuscript preparation. The VESTA program53 was used to visualize the experimental and DFT crystal structures and electronic densities. The authors thank Prof. Sudo and Mr. Kitao of Kindai University for their help in the solid state NMR measurement. This work was partially supported by a Grant-in-Aid for Scientific Research on Innovative Area “Mixed Anion (Project JP17H05489, JP19H04706)” (JSPS). The synchrotron radiation experiments were performed at the BL02B2 of SPring-8 with the approval of the Japan Synchrotron Radiation Research Institute (JASRI) (Proposal No. 2016A1157 and 2018A1227). Theab initiocalculations were performed with the computational resources of the Research Center for Advanced Computing Infrastructure (RCACI) at JAIST. The authors gratefully thank Division of Joint Research Center, Kindai University, for the solid-state NMR measurements. T. I. and F. A. R. acknowledge support from US Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division. K. O. is grateful for financial support from Kansai Research Foundation for technology promotion and a Grant-in-Aids for Scientific Research (C) (Project JP16K05731 and 21K04659). K. H. is grateful for financial support from MEXT-KAKENHI (JP19K05029, JP21K03400, JP21H01998, and JP22H02170), and the Air Force Office of Scientific Research (Award Numbers: FA2386-20-1-4036). R. M. is grateful for financial supports from MEXT-KAKENHI (22H05146, 21K03400 and 19H04692), from the Air Force Office of Scientific Research (AFOSR-AOARD/FA2386-17-1-4049;FA2386-19-1-4015), and from JSPS Bilateral Joint Projects (JPJSBP120197714). The authors acknowledge Erica Heinrich for valuable help with manuscript preparation. The VESTA program53 was used to visualize the experimental and DFT crystal structures and electronic densities. The authors thank Prof. Sudo and Mr. Kitao of Kindai University for their help in the solid state NMR measurement. This work was partially supported by a Grant-in-Aid for Scientific Research on Innovative Area “Mixed Anion (Project JP17H05489, JP19H04706)” (JSPS). The synchrotron radiation experiments were performed at the BL02B2 of SPring-8 with the approval of the Japan Synchrotron Radiation Research Institute (JASRI) (Proposal No. 2016A1157 and 2018A1227). The ab initio calculations were performed with the computational resources of the Research Center for Advanced Computing Infrastructure (RCACI) at JAIST. The authors gratefully thank Division of Joint Research Center, Kindai University, for the solid-state NMR measurements. T. I. and F. A. R. acknowledge support from US Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division. K. O. is grateful for financial support from Kansai Research Foundation for technology promotion and a Grant-in-Aids for Scientific Research (C) (Project JP16K05731 and 21K04659). K. H. is grateful for financial support from MEXT-KAKENHI (JP19K05029, JP21K03400, JP21H01998, and JP22H02170), and the Air Force Office of Scientific Research (Award Numbers: FA2386-20-1-4036). R. M. is grateful for financial supports from MEXT-KAKENHI (22H05146, 21K03400 and 19H04692), from the Air Force Office of Scientific Research (AFOSR-AOARD/FA2386-17-1-4049;FA2386-19-1-4015), and from JSPS Bilateral Joint Projects (JPJSBP120197714).

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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.",

author = "Kengo Oka and Tom Ichibha and Daichi Kato and Yasuto Noda and Yusuke Tominaga and Kosei Yamada and Mitsunobu Iwasaki and Naoki Noma and Kenta Hongo and Ryo Maezono and Reboredo, \{Fernando A.\}",

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AU - Oka, Kengo

AU - Ichibha, Tom

AU - Kato, Daichi

AU - Noda, Yasuto

AU - Tominaga, Yusuke

AU - Yamada, Kosei

AU - Iwasaki, Mitsunobu

AU - Noma, Naoki

AU - Hongo, Kenta

AU - Maezono, Ryo

AU - Reboredo, Fernando A.

PY - 2022/11/28

Y1 - 2022/11/28

N2 - 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.

AB - 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.

UR - https://www.scopus.com/pages/publications/85140081923

U2 - 10.1039/d2dt00839d

DO - 10.1039/d2dt00839d

M3 - Article

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AN - SCOPUS:85140081923

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JO - Dalton Transactions

JF - Dalton Transactions

IS - 40

ER -

Anionic ordering in Pb₂Ti₄O₉F₂revisited by nuclear magnetic resonance and density functional theory

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