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@ARTICLE{Jafari:454537,
author = {Jafari, Atefeh and Klobes, Benedikt and Sergeev, Ilya and
Moseley, Duncan H. and Manley, Michael E. and Dronskowski,
Richard and Deringer, Volker L. and Stoffel, Ralf P. and
Bessas, Dimitrios and Chumakov, Aleksandr I. and Rüffer,
Rudolf and Mahmoud, Abdelfattah and Bridges, Craig A. and
Daemen, Luke L. and Cheng, Yongqiang and Ramirez-Cuesta,
Anibal J. and Hermann, Raphael P.},
title = {{P}honon {S}pectroscopy in {A}ntimony and {T}ellurium
{O}xides},
journal = {The journal of physical chemistry / A},
volume = {124},
number = {39},
issn = {1520-5215},
address = {Washington, DC},
publisher = {Soc.},
reportid = {PUBDB-2021-00588},
pages = {7869 - 7880},
year = {2020},
note = {Waiting for fulltext},
abstract = {α-Sb2O3 (senarmontite), β-Sb$_2$O$_3$ (valentinite), and
α-TeO$_2$ (paratellurite) are compounds with pronounced
stereochemically active Sb and Te lone pairs. The
vibrational and lattice properties of each have been
previously studied but often lead to incomplete or
unreliable results due to modes being inactive in infrared
or Raman spectroscopy. Here, we present a study of the
relationship between bonding and lattice dynamics of these
compounds. Mössbauer spectroscopy is used to study the
structure of Sb in α-Sb$_2$O$_3$ and β-Sb$_2$O$_3$,
whereas the vibrational modes of Sb and Te for each oxide
are investigated using nuclear inelastic scattering, and
further information on O vibrational modes is obtained using
inelastic neutron scattering. Additionally, vibrational
frequencies obtained by density functional theory (DFT)
calculations are compared with experimental results in order
to assess the validity of the utilized functional. Good
agreement was found between DFT-calculated and experimental
density of phonon states with a 7\% scaling factor. The
Sb–O–Sb wagging mode of α-Sb$_2$O$_3$ whose frequency
was not clear in most previous studies is experimentally
observed for the first time at ∼340 cm$^{–1}$. Softer
lattice vibrational modes occur in orthorhombic
β-Sb$_2$O$_3$ compared to cubic α-Sb$_2$O$_3$, indicating
that the antimony bonds are weakened upon transforming from
the molecular α phase to the layer-chained β structure.
The resulting vibrational entropy increase of 0.45 ± 0.1
k$_B$/Sb$_2$O$_3$ at 880 K accounts for about half of the
α–β transition entropy. The comparison of experimental
and theoretical approaches presented here provides a
detailed picture of the lattice dynamics in these oxides
beyond the zone center and shows that the accuracy of DFT is
sufficient for future calculations of similar material
structures.},
cin = {DOOR ; HAS-User / FS-PET-S},
ddc = {530},
cid = {I:(DE-H253)HAS-User-20120731 /
I:(DE-H253)FS-PET-S-20190712},
pnm = {6212 - Quantum Condensed Matter: Magnetism,
Superconductivity (POF3-621) / 6G3 - PETRA III (POF3-622)},
pid = {G:(DE-HGF)POF3-6212 / G:(DE-HGF)POF3-6G3},
experiment = {EXP:(DE-H253)P-P01-20150101},
typ = {PUB:(DE-HGF)16},
pubmed = {pmid:32894948},
UT = {WOS:000577149400002},
doi = {10.1021/acs.jpca.0c05060},
url = {https://bib-pubdb1.desy.de/record/454537},
}