Disproportionation of SO_{2} at High Pressure and Temperature

Materials once suffered at high-pressure and high-temperature (HPHT) conditions often exhibit exotic phenomena that defy conventional wisdom. The behaviors of sulfur dioxide (SO_{2}), one of the archetypal simple molecules, at HPHT conditions have attracted a great deal of attention due to its relevance to the S cycle between deep Earth and the atmosphere. Here we report the discovery of an unexpected disproportionation of SO_{2} via bond breaking into elemental S and sulfur trioxide (SO_{3}) at HPHT conditions through a jointly experimental and theoretical study. Measured x-ray diffraction and Raman spectroscopy data allow us to solve unambiguously the crystal structure (space group R3[over ¯]c) of the resultant SO_{3} phase that shows an extended framework structure formed by vertex-sharing octahedra SO_{6}. Our findings lead to a significant extension of the phase diagram of SO_{2} and suggest that SO_{2}, despite its abundance in Earth's atmosphere and ubiquity in other giant planets, is not a stable compound at HPHT conditions relevant to planetary interiors, providing important implications for elucidating the S chemistry in deep Earth and other giant planets.