It is commonly believed that electromagnetic spectra of atoms and molecules can be fully described by interactions involving electric and magnetic multipoles. However, it has recently become clear that interactions between light and matter also involve toroidal multipoles-toroidal absorption lines have been observed in electromagnetic metamaterials. Here, we show that a previously unexplored type of spectroscopy of the hitherto largely neglected toroidal dipolar interaction becomes feasible if, apart from the classical r × r × p toroidal dipole density term responsible for the toroidal transitions in metamaterials, the spin-dependent r × σ term (which only occurs in relativistic quantum mechanics) is taken into account. Toroidal dipole operators are odd under parity and time-reversal symmetries; toroidal dipole transitions can therefore be distinguished from electric multipole and magnetic dipole transitions.