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

Mullens, BG; Marlton, FP; Nicholas, MK; Permana, AJ; Avdeev, M; Mukherjee, S; Vaitheeswaran, G; Li, C; Liu, J; Chater, PA; Kennedy, BJ

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

Mullens, BG Marlton, FP Nicholas, MK Permana, AJ Avdeev, M Mukherjee, S Vaitheeswaran, G Li, C Liu, J Chater, PA Kennedy, BJ

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Publisher:: AMER CHEMICAL SOC
Publication Type:: Journal Article
Citation:: Inorg Chem, 2024, 63, (24), pp. 11176-11186
Issue Date:: 2024-06-17

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Field	Value	Language
dc.contributor.author	Mullens, BG
dc.contributor.author	Marlton, FP
dc.contributor.author	Nicholas, MK
dc.contributor.author	Permana, AJ
dc.contributor.author	Avdeev, M
dc.contributor.author	Mukherjee, S
dc.contributor.author	Vaitheeswaran, G
dc.contributor.author	Li, C
dc.contributor.author	Liu, J
dc.contributor.author	Chater, PA
dc.contributor.author	Kennedy, BJ
dc.date.accessioned	2025-01-16T04:30:08Z
dc.date.available	2025-01-16T04:30:08Z
dc.date.issued	2024-06-17
dc.identifier.citation	Inorg Chem, 2024, 63, (24), pp. 11176-11186
dc.identifier.issn	0020-1669
dc.identifier.issn	1520-510X
dc.identifier.uri	http://hdl.handle.net/10453/183776
dc.description.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.
dc.format	Print-Electronic
dc.language	eng
dc.publisher	AMER CHEMICAL SOC
dc.relation.ispartof	Inorg Chem
dc.relation.isbasedon	10.1021/acs.inorgchem.4c00866
dc.rights	info:eu-repo/semantics/closedAccess
dc.subject	0302 Inorganic Chemistry, 0306 Physical Chemistry (incl. Structural), 0399 Other Chemical Sciences
dc.subject.classification	Inorganic & Nuclear Chemistry
dc.subject.classification	3402 Inorganic chemistry
dc.subject.classification	3403 Macromolecular and materials chemistry
dc.title	Seeing the Unseen: The Structural Influence of the Lone Pair Electrons in PbWO4.
dc.type	Journal Article
utslib.citation.volume	63
utslib.location.activity	United States
utslib.for	0302 Inorganic Chemistry
utslib.for	0306 Physical Chemistry (incl. Structural)
utslib.for	0399 Other Chemical Sciences
pubs.organisational-group	University of Technology Sydney
pubs.organisational-group	University of Technology Sydney/Faculty of Science
pubs.organisational-group	University of Technology Sydney/Faculty of Science/School of Mathematical and Physical Sciences
utslib.copyright.status	closed_access	*
dc.date.updated	2025-01-16T04:30:06Z
pubs.issue	24
pubs.publication-status	Published
pubs.volume	63
utslib.citation.issue	24

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.

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http://hdl.handle.net/10453/183776