Molecular and polymeric amorphous forms in dense SO$_2$

Abstract: We report here a study of reversible pressure-induced structural transformation between two amorphous forms of SO$_2$: molecular at pressures below 26 GPa and polymeric above this pressure, at temperatures of 77 - 300 K. The transformation was observed by Raman spectroscopy and x-ray diffraction in a diamond anvil cell. The same phenomenon was also observed in ab initio molecular dynamics simulations where both forward and reverse transitions were detected, allowing to analyze in detail the atomic structure of both phases. The high-pressure polymeric amorphous form was found to consist mainly of disordered polymeric chains made of 3-coordinated sulfur atoms connected via oxygen atoms, and few residual intact molecules. The simulation results are in good agreement with experimental data. Our observations suggest a possible existence of molecular liquid - polymeric liquid transition in SO$_2$ and show a case example of polyamorphism in system consisting of simple molecules with multiple bonds.