The direct adjustment of two-component pseudopotentials (scalar-relativistic + spin-orbit potentials), to atomic total energy valence spectra derived from four-component multiconfiguration Dirac-Hartree-Fock all-electron calculations based on the Dirac-Coulomb-Breit Hamiltonian, has been made a routine tool for an efficient treatment of heavy main-group elements. Both large-core (nsp valence shell) and small-core ((n - 1)spd nsp valence shell) potentials have been generated for all the post-d elements of groups 13-17. At the example of lead and bismuth compounds (PbHal, BiH, BiO, BiHal (Hal = F, Cl, Br, I)), we show how small-core and large-core potentials can be combined in accurate, yet computationally economic, spin-free-state-shifted relativistic electronic structure calculations of molecular ground and excited states.