Seeing the Unseen: The Structural Influence of the Lone Pair Electrons in PbWO4

Bryce G. Mullens; Frederick P. Marlton; Maria K. Nicholas; Ahmadi Jaya Permana; Maxim Avdeev; Supratik Mukherjee; Ganapathy Vaitheeswaran; Cheng Li; Jue Liu; Philip A. Chater; Brendan J. Kennedy

doi:10.1021/acs.inorgchem.4c00866

Seeing the Unseen: The Structural Influence of the Lone Pair Electrons in PbWO₄

Bryce G. Mullens
, Frederick P. Marlton
, Maria K. Nicholas
, Ahmadi Jaya Permana
, Maxim Avdeev
, Supratik Mukherjee
, Ganapathy Vaitheeswaran
, Cheng Li
, Jue Liu
, Philip A. Chater
, Brendan J. Kennedy

Powder Diffraction

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

4 Scopus citations

Abstract

Pair distribution function (PDF) analysis of the scheelite-type material PbWO₄ reveals previously unidentified short-range structural distortions in the PbO₈ polyhedra and WO₄ tetrahedra not observed in the similarly structured CaWO₄. These local distortions are a result of the structural influence of the Pb²⁺ 6s² lone pair electrons. These are not evident from the Rietveld analysis of synchrotron X-ray or neutron powder diffraction data, nor do they strongly influence the X-ray PDF (XPDF). This illustrates the importance of neutron PDF (NPDF) in the study of such materials. First-principles density function theory (DFT) calculations show that the Pb²⁺ 6s² electrons are hybridized with the O^2- 2p electrons near the Fermi level. The presence of local-scale distortions has previously been neglected in studies of structure-functionality relationships in PbWO₄ and other scheelite-structured photocatalytic materials, including BiVO₄, and this observation opens new avenues for their optimization.

Original language	English
Pages (from-to)	11176-11186
Number of pages	11
Journal	Inorganic Chemistry
Volume	63
Issue number	24
DOIs	https://doi.org/10.1021/acs.inorgchem.4c00866
State	Published - Jun 17 2024

Funding

We acknowledge the support of the Australian Research Council for this work that was facilitated by access to Sydney Analytical, a core research facility at the University of Sydney and was in part undertaken at the Australian Centre for Neutron Scattering (P13946) and at the powder diffraction beamline (M18941) of the Australian Synchrotron with the assistance of Dr Helen Brand. Bryce G. Mullens thanks the Australian Institute for Nuclear Science and Engineering for a PGRA scholarship. S.M. is grateful for the financial support provided by DRDO, India, through ACRHEM (DRDO/18/1801/2016/01038: ACRHEM-PHASE-III). G.V would like to acknowledge Institute of Eminence, University of Hyderabad (UOH-IOE-RC3-21-046) funding and CMSD, for providing the computational facilities, A portion of this research used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory (IPTS#29995.1). Work at Oak Ridge National Laboratory was supported by the US Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division, under contract no. DE-AC05-00OR22725D.

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10.1021/acs.inorgchem.4c00866

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title = "Seeing the Unseen: The Structural Influence of the Lone Pair Electrons in PbWO4",

abstract = "Pair distribution function (PDF) analysis of the scheelite-type material PbWO4 reveals previously unidentified short-range structural distortions in the PbO8 polyhedra and WO4 tetrahedra not observed in the similarly structured CaWO4. These local distortions are a result of the structural influence of the Pb2+ 6s2 lone pair electrons. These are not evident from the Rietveld analysis of synchrotron X-ray or neutron powder diffraction data, nor do they strongly influence the X-ray PDF (XPDF). This illustrates the importance of neutron PDF (NPDF) in the study of such materials. First-principles density function theory (DFT) calculations show that the Pb2+ 6s2 electrons are hybridized with the O2- 2p electrons near the Fermi level. The presence of local-scale distortions has previously been neglected in studies of structure-functionality relationships in PbWO4 and other scheelite-structured photocatalytic materials, including BiVO4, and this observation opens new avenues for their optimization.",

author = "Mullens, \{Bryce G.\} and Marlton, \{Frederick P.\} and Nicholas, \{Maria K.\} and Permana, \{Ahmadi Jaya\} and Maxim Avdeev and Supratik Mukherjee and Ganapathy Vaitheeswaran and Cheng Li and Jue Liu and Chater, \{Philip A.\} and Kennedy, \{Brendan J.\}",

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doi = "10.1021/acs.inorgchem.4c00866",

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T2 - The Structural Influence of the Lone Pair Electrons in PbWO4

AU - Mullens, Bryce G.

AU - Marlton, Frederick P.

AU - Nicholas, Maria K.

AU - Permana, Ahmadi Jaya

AU - Avdeev, Maxim

AU - Mukherjee, Supratik

AU - Vaitheeswaran, Ganapathy

AU - Li, Cheng

AU - Liu, Jue

AU - Chater, Philip A.

AU - Kennedy, Brendan J.

PY - 2024/6/17

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N2 - Pair distribution function (PDF) analysis of the scheelite-type material PbWO4 reveals previously unidentified short-range structural distortions in the PbO8 polyhedra and WO4 tetrahedra not observed in the similarly structured CaWO4. These local distortions are a result of the structural influence of the Pb2+ 6s2 lone pair electrons. These are not evident from the Rietveld analysis of synchrotron X-ray or neutron powder diffraction data, nor do they strongly influence the X-ray PDF (XPDF). This illustrates the importance of neutron PDF (NPDF) in the study of such materials. First-principles density function theory (DFT) calculations show that the Pb2+ 6s2 electrons are hybridized with the O2- 2p electrons near the Fermi level. The presence of local-scale distortions has previously been neglected in studies of structure-functionality relationships in PbWO4 and other scheelite-structured photocatalytic materials, including BiVO4, and this observation opens new avenues for their optimization.

AB - Pair distribution function (PDF) analysis of the scheelite-type material PbWO4 reveals previously unidentified short-range structural distortions in the PbO8 polyhedra and WO4 tetrahedra not observed in the similarly structured CaWO4. These local distortions are a result of the structural influence of the Pb2+ 6s2 lone pair electrons. These are not evident from the Rietveld analysis of synchrotron X-ray or neutron powder diffraction data, nor do they strongly influence the X-ray PDF (XPDF). This illustrates the importance of neutron PDF (NPDF) in the study of such materials. First-principles density function theory (DFT) calculations show that the Pb2+ 6s2 electrons are hybridized with the O2- 2p electrons near the Fermi level. The presence of local-scale distortions has previously been neglected in studies of structure-functionality relationships in PbWO4 and other scheelite-structured photocatalytic materials, including BiVO4, and this observation opens new avenues for their optimization.

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EP - 11186

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 24

ER -

Seeing the Unseen: The Structural Influence of the Lone Pair Electrons in PbWO₄

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