Structural, Vibrational, and Electronic Study of Sb2S3 at High Pressure

Antimony trisulfide (Sb2S3), found in nature as the mineral stibnite, has been studied under compression at room temperature from a joint experimental and theoretical perspective. X-ray diffraction and Raman scattering measurements are complemented with ab initio total-energy, lattice-dynamics, and electronic structure calculations. The continuous changes observed in the volume, lattice parameters, axial ratios, bond lengths, and Raman mode frequencies as a function of pressure can be attributed to the different compressibility along the three orthorhombic axes in different pressure ranges, which in turn are related to the different compressibility of several interatomic bond distances in different pressure ranges. The structural and vibrational properties of Sb2S3 under compression are compared and discussed in relation to isostructural Bi2S3 and Sb2Se3. No first-order phase transition has been observed in Sb2S3 up to 25 GPa, in agreement with the stability of the Pnma structure in Bi2S3 and Sb2Se3 previously reported up to 50 GPa. Our measurements and calculations do not show evidence either for a pressure-induced second-order isostructural phase transition or for an electronic topological transition in Sb2S3.This work has been performed under financial support from Spanish MINECO under Projects MAT2013-46649-C4-2/3-P and MAT2015-71070-REDC. This publication is fruit of "Programa de Valoracion y Recursos Conjuntos de I+D+i VLC/CAMPUS" and has been financed by the Spanish Ministerio de Educacion, Cultura y Deporte, as part of "Programa Campus de Excelencia Internacional" through Projects SP20140701 and SP20140871. These experiments were performed at BL04-MSPD beamline at ALBA Synchrotron with the collaboration of ALBA staff. Supercomputer time has been provided by the Red Espanola de Supercomputacion (RES) and the MALTA cluster. J.A.S. acknowledges financial support through Juan de la Cierva fellowship.Ibáñez, J.; Sans-Tresserras, JÁ.; Popescu, C.; López-Vidrier, J.; Elvira-Betanzos, J.; Cuenca Gotor, VP.; Gomis, O.... (2016). Structural, Vibrational, and Electronic Study of Sb2S3 at High Pressure. Journal of Physical Chemistry C. 19(120):10547-10558. doi:10.1021/acs.jpcc.6b01276S10547105581912