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The basis sets for the occupied spinors were optimized at the Dirac\u2013Coulomb self-consistent field level on the ground configurations. Valence and core correlating functions were optimized in multireference SDCI calculations on the ground configuration. Diffuse functions optimized on the anion (or derived from neighboring elements for group 18) are also provided. Basic atomic and molecular properties were used to test the newly developed basis sets. A smooth convergence to the basis set limit is observed with increased basis set quality from the previously available double-zeta, triple-zeta, and quadruple-zeta basis sets to the newly developed quintuple-zeta basis sets for the calculated molecular bond lengths and dissociation energies and for atomic ionization potentials and electron affinities. The use of these basis sets in combination with state-of-the-art approaches for the treatment of relativity and correlation will allow significantly increased accuracy in calculations on the heavy elements and their compounds. 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