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@ARTICLE{Alderman:148574,
author = {Alderman, O. L. G. and Hannon, A. C. and Holland, D. and
Feller, S. and Lehr, G. and Vitale, A. J. and Hoppe, U. and
Zimmermann, M. V. and Watenphul, A. and DESY},
title = {{L}one-{P}air {D}istribution and {P}lumbite {N}etwork
{F}ormation in {H}igh {L}ead {S}ilicate {G}lass,
$80{P}b_{{O}.20}{S}i{O}_2$},
journal = {Physical Chemistry Chemical Physics},
volume = {15},
issn = {1463-9076},
address = {Cambridge},
publisher = {RSC Publ.},
reportid = {PHPPUBDB-26509},
pages = {8506-8519},
year = {2013},
note = {(c) the Owner Societies},
abstract = {For the first time a detailed structural model has been
determined which shows how the lone-pairs of electrons are
arranged relative to each other in a glass network
containing lone-pair cations. High energy X-ray and neutron
diffraction patterns of a very high lead content silicate
glass (80PbO·20SiO2) have been used to build
three-dimensional models using empirical potential structure
refinement. Coordination number and bond angle distributions
reveal structural similarity to crystalline Pb11Si3O17 and
α- and β-PbO, and therefore strong evidence for a plumbite
glass network built from pyramidal [PbOm] polyhedra (m∼
3-4), with stereochemically active lone-pairs, although with
greater disorder in the first coordination shell of lead
compared to the first coordination shell of silicon. The
oxygen atoms are coordinated predominantly to four cations.
Explicit introduction of lone-pair entities into some models
leads to modification of the local Pb environment, whilst
still allowing for reproduction of the measured diffraction
patterns, thus demonstrating the non-uniqueness of the
solutions. Nonetheless, the models share many features with
crystalline Pb11Si3O17, including the O-Pb-O bond angle
distribution, which is more highly structured than reported
for lower Pb content glasses using reverse Monte Carlo
techniques. The lone-pair separation of 2.85 Å in the model
glasses compares favourably with that estimated in α-PbO as
2.88 Å, and these lone-pairs organise to create voids in
the glass, just as they create channels in Pb11Si3O17 and
interlayer spaces in the PbO polymorphs.},
cin = {FS-DO / DOOR},
ddc = {540},
cid = {I:(DE-H253)FS-DO-20120731 / I:(DE-H253)HAS-User-20120731},
pnm = {DORIS Beamline BW5 (POF1-550)},
pid = {G:(DE-H253)POF1-BW5-20130405},
experiment = {EXP:(DE-H253)D-BW5-20150101},
typ = {PUB:(DE-HGF)16},
pubmed = {pmid:23657606},
UT = {WOS:000319006100008},
doi = {10.1039/c3cp51348c},
url = {https://bib-pubdb1.desy.de/record/148574},
}