Redetermination of crystal structure of Ag(II)SO4 and its high-pressure behavior up to 30 GPa

Here we redetermine the crystal structure of Ag(II)SO4, an unusual d(9) system, at 1 atm from powder X-ray data and we report hydrostatic pressure X-ray diffraction experiments on Ag(II)SO4 inside the diamond anvil cell. AgSO4 crystallizes in the monoclinic C2/c cell, with a = 12.8476(2) angstrom, b = 13.6690(4) angstrom, c = 9.36678(19) angstrom, beta = 47.5653(13)degrees, and V = 1214.04(5) angstrom(3) (Z = 16). AgSO4 exhibits bulk modulus, B-0, of 36.9 GPa, and undergoes sluggish decomposition at similar to 23 GPa yielding a high-pressure phase of Ag2S2O7 (K2S2O7-type), with the substrate and product coexisting at 30 GPa. Theoretical calculations within Density Functional Theory for the C2/c cell nicely reproduce the observed trend for lattice constants as well as the B-0 values of AgSO4, and suggest that the rigidity of the infinite [Ag(SO4)] chains as well as the Jahn-Teller effect for the Ag(II) cation persist even at 30 GPa.