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Compressibility of β-As4S4: an in situ high-pressure single-crystal X-ray study

Published online by Cambridge University Press:  05 July 2018

G. O. Lepore
Affiliation:
Dipartimento di Scienze della Terra, Università degli Studi di Firenze, Via G. La Pira 4, I-50121 Firenze, Italy
T. Boffa Ballaran
Affiliation:
Bayerisches Geoinstitut, Universität Bayreuth, Bayreuth, D-95440, Germany
F. Nestola
Affiliation:
Dipartimento di Geoscienze, Università degli Studi di Padova, Via Gradenigo 6, I-35131 Padova, Italy
L. Bindi
Affiliation:
Museo di Storia Naturale, Sezione di Mineralogia e Litologia, Università degli Studi di Firenze, Via G. La Pira 4, I-50121 Firenze, Italy
D. Pasqual
Affiliation:
Dipartimento di Geoscienze, Università degli Studi di Padova, Via Gradenigo 6, I-35131 Padova, Italy
P. Bonazzi*
Affiliation:
Dipartimento di Scienze della Terra, Università degli Studi di Firenze, Via G. La Pira 4, I-50121 Firenze, Italy

Abstract

Ambient temperature X-ray diffraction data were collected at different pressures from two crystals of β-As4S4, which were made by heating realgar under vacuum at 295ºC for 24 h. These data were used to calculate the unit-cell parameters at pressures up to 6.86 GPa. Above 2.86 GPa, it was only possible to make an approximate measurement of the unit-cell parameters. As expected for a crystal structure that contains molecular units held together by weak van der Waals interactions, β-As4S4 has an exceptionally high compressibility. The compressibility data were fitted to a third-order Birch–Murnaghan equation of state with a resulting volume V0 = 808.2(2) Å3, bulk modulus K0 = 10.9(2) GPa and K' = 8.9(3). These values are extremely close to those reported for the low-temperature polymorph of As4S4, realgar, which contains the same As4S4 cage-molecule. Structural analysis showed that the unit-cell contraction is due mainly to the reduction in intermolecular distances, which causes a substantial reduction in the unit-cell volume (∼21% at 6.86 GPa). The cage-like As4S4 molecules are only slightly affected. No phase transitions occur in the pressure range investigated.

Micro-Raman spectra, collected across the entire pressure range, show that the peaks associated with As–As stretching have the greatest pressure dependence; the S–As–S bending frequency and the As–S stretching have a much weaker dependence or no variation at all as the pressure increases; this is in excellent agreement with the structural data.

Type
Research Article
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2012

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