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

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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

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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.}",

note = "Publisher Copyright: {\textcopyright} 2024 American Chemical Society.",

year = "2024",

month = jun,

day = "17",

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

language = "English",

volume = "63",

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journal = "Inorganic Chemistry",

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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

Y1 - 2024/6/17

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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U2 - 10.1021/acs.inorgchem.4c00866

DO - 10.1021/acs.inorgchem.4c00866

M3 - Article

AN - SCOPUS:85193705218

SN - 0020-1669

VL - 63

SP - 11176

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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