The Importance of Tight f Basis Functions for Heavy p-Block Oxides and Halides: A Parallel With Tight d functions in the Second Row

It is well-known that both wave function ab initio and DFT calculations on second-row compounds exhibit anomalously slow basis set convergence unless the basis sets are augmented with additional tight (high-exponent) d functions, as in the cc-pV(n+d)Z and aug-cc-pV(n+d)Z basis sets. This has been rationalized as being necessary for a better description of the low-lying 3d orbital, which as the oxidation state increases sinks low enough to act as a back-donation acceptor from chalcogen and halogen lone pairs. This prompts the question whether a similar phenomenon exists for the isovalent compounds of the heavy p-block. We show that for the fourth and fifth row, this is the case, but this time for tight f functions enhancing the description of the low-lying 4f and 5f Rydberg orbitals, respectively. In the third-row heavy p block, the 4f orbitals are too far up, while the 4d orbitals are adequately covered by the basis functions already present to describe the 3d subvalence orbitals.

Automated summary

It is necessary to use additional tight (high-exponent) d functions in wave function ab initio and DFT calculations for second-row compounds, such as the cc-pV(n+d)Z and aug-cc-pV(n+d)Z basis sets, to achieve proper convergence. A similar phenomenon exists for the isovalent compounds of the heavy p-block, where tight f functions are needed to enhance the description of the low-lying 4f and 5f Rydberg orbitals.