All-electron segmented contraction basis sets of triple zeta valence quality for the fifth-row elements

All-electron contracted Gaussian basis set of triple zeta valence quality plus polarisation functions (TZP) for the elements Cs, Ba, La, and from Hf to Rn is presented. Douglas–Kroll–Hess (DKH) basis set for fifth-row elements is also reported. We have recontracted the original TZP basis set, i.e., the values of the contraction coefficients are re-optimised using the second-order DKH Hamiltonian. By addition of diffuse functions (s, p, d, f, and g symmetries), which are optimised for the anion ground states, an augmented TZP basis set is constructed. Using the B3LYP hybrid functional, the performance of the TZP–DKH basis set is assessed for predicting atomic ionisation energy as well as spectroscopy constants of some compounds. Despite its compact size, this set demonstrates consistent, efficient, and reliable performance and will be especially useful in calculations of molecular properties that require explicit treatment of the core electrons.