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

  • G. O. Lepore (a1), T. Boffa Ballaran (a2), F. Nestola (a3), L. Bindi (a4), D. Pasqual (a3) and P. Bonazzi (a1)...

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.

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Angel, R.J. (2000) Equations of State. Pp. 3559 in: High-Temperature and High-Pressure Crystal Chemistry (R.M. Hazen and R.T. Downs, editors). Reviews in Mineralogy and Geochemistry, 41. Mineralogical Society of America, Washington DC and the Geochemical Society, St Louis, Missouri, USA.
Angel, R.J. and Finger, L.W. (2011) SINGLE: a program to control single-crystal diffractometers. Journal of Applied Crystallography, 44, 247251.
Angel, R.J., Allan, D.R., Miletich, R. and Finger, L.W. (1997) The use of quartz as an internal pressure standard in high-pressure crystallography. Journal of Applied Crystallography, 30, 461466.
Angel, R.J., Downs, R.T. and Finger, L.W. (2000) High-pressure, high-temperature diffractometry. Pp. 559596 in: High-Temperature and High-Pressure Crystal Chemistry (RM. Hazen and R.T. Downs, editors). Reviews in Mineralogy and Geochemistry, 41. Mineralogical Society of America, Washington DC and the Geochemical Society, St Louis, Missouri, USA.
Angel, R.J., Bujak, M., Zhao, J., Gatta, G.D. and Jacobsen, S.D. (2007) Effective hydrostatic limits of pressure media for high-pressure crystallographic studies. Journal of Applied Crystallography, 40, 2632.
Balic-Zunic, T. and Vickovic, I. (1996) IVTON- a program for the calculation of geometrical aspects of crystal structures and some crystal chemical applications. Journal of Applied Crystallography, 29, 305306.
Bonazzi, P and Bindi, L. (2008) A crystallographic review of arsenic sulfides: effects of chemical variations and changes induced by light exposure. Zeitschrift fur Kristallographie, 223, 132147.
Bonazzi, P., Menchetti, S., Pratesi, G, Muniz-Miranda, M. and Sbrana, G (1996) Light-induced variations in realgar and [3-As4S4: X-ray diffraction and Raman studies. American Mineralogist, 81, 874880.
Bonazzi, P., Bindi, L., Pratesi, G and Menchetti, S. (2006) Light-induced changes in molecular arsenic sulfides: state of the art and new evidence by single-crystal X-ray diffraction. American Mineralogist, 91, 13231330.
Bondi, A. (1964) Van der Waals volumes and radii. Journal of Physical Chemistry, 68, 441452.
Chattopadhyay, T., Werner, A. and von Schnering, H.G (1982) Thermal expansion and compressibility of fS-As4S3 . Journal of Physics and Chemistry of Solids, 48, 919923.
Hejny, C, Sagl, R., Tobbens, D.M., Miletich, R., Wildner, M., Nasdala, L., Ullrich, A. and Balic-Zunic, T. (2012) Crystal-structure properties and the molecular nature of hydrostatically compressed realgar. Physics and Chemistry of Minerals, 39, 399412.
Ibers, J.A. and Hamilton, W.C. (editors) (1974) International Tables for X-ray Crystallography, vol. IV. Kynock Press, Birmingham, UK.
Jeanloz, R. and Hazen, R.M. (1991) Finite-strain analysis of relative compressibilities. Application to the high-pressure wadsleyite phase as an illustration. American Mineralogist, 76, 17651768.
King, H.E. and Finger, L.W. (1979) Diffracted beam crystal centering and its application to high-pressure crystallography. Journal of Applied Crystallography, 12, 374378.
Kolobov, A.V. (editor) (2003) Photo-Induced Metastability in Amorphous Semiconductors. Wiley—VCH, Weinheim, Germany, 415 pp.
Mao, H.K., Xu, J. and Bell, P.M. (1986) Calibration of the ruby pressure gauge to 800 kbar under quasi-hydrostatic conditions. Journal of Geophysical Research, 91, 46734676.
Muniz-Miranda, M., Sbrana, G, Bonazzi, P., Menchetti, S. and Pratesi, G (1996) Spectroscopic investigation and normal mode analysis of As4S4 polymorphs. Spectrochimica Acta, A52, 13911401.
Oxford Diffraction (2006) CrysAlis RED (version 1.171.31.2). Oxford Diffraction Ltd, Abingdon, Oxfordshire, UK.
Porter, E.J. and Sheldrick, G.M. (1972) Crystal structure of a new crystalline modification of tetra-arsenic tetrasulphide (2,4,6,8-tetrathia-1,3,5,7-tetra-arsatri-cyclo[3,3,0,03,7]-octane). Journal of the Chemical Society, Dalton Transactions, 13, 13471349.
Sheldrick, G.M. (2008) A short history of SHELX. Acta Crystallographica, A64, 112122.
Stoe and Cie (2008) X-RED32 and X-SHAPE. Stoe and Cie, Darmstadt, Germany.
Tuktabiev, M.A., Popova, S.V., Brazhkin, V.V., Lyapin, A.G and Katayama, Y. (2009) Compressibility and polymorphism of a-As4S4 realgar under high pressure. Journal of Physics: Condensed Matter, 21, http://dx.doi.org/10.1088/0953-8984/21/38/385401.

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

  • G. O. Lepore (a1), T. Boffa Ballaran (a2), F. Nestola (a3), L. Bindi (a4), D. Pasqual (a3) and P. Bonazzi (a1)...

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