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We have studied the amorphization process of SnI4 up to 26.8GPa with unprecedented experimental details by combining Sn and I K edge X-ray absorption spectroscopy and powder X-ray diffraction. Standards and reverse Monte Carlo extended X-ray absorption fine structure (EXAFS) refinements confirm that the SnI4 tetrahedron is a fundamental structural unit that is preserved through the crystalline phase-I to crystalline phase-II transition about 7 to 10GPa and then in the amorphous phase that appears above 20GPa. Up to now unexploited Iodine EXAFS reveals to be extremely informative and confirms the formation of iodine iodine short bonds close to 2.85A in the amorphous phase at 26.8 GPa. A coordination number increase of Sn in the crystalline phase-II appears to be excluded, while the deformation of the tetrahedral units proceeds through a flattening that keeps the average I-Sn-I angle close to 109.5°. Moreover, we put in evidence the impact of pressure on the Sn near edge structure under competing geometrical and electronic effects.

Mechanism of pressure induced amorphization of SnI4: A combined x-ray diffraction—x-ray absorption spectroscopy study