How should one add diffuse functions to the basis set? Diffuse functions are known to be critical in describing the electron distribution of anions (as discussed in my book), but they are also quite important in describing weak interactions, like hydrogen bonds, and can be critical in evaluating activation barriers and other properties.

The Truhlar group has been active in benchmarking the need of basis functions and their recent review1 summarizes their work. In particular, they recommend that for DFT computations a minimally augmented basis set is appropriate for examining barrier heights and weakly bound systems. A minimally augmented basis set would have s and p diffuse functions on heavy atoms for the Pople split-valence basis sets and the Dunning cc-pVxZ basis sets.

For wavefunction based computations, they recommend the use of the “jun-“ basis sets. The “jun” basis set is one of the so-called calendar basis set derived from the aug-cc-pVxZ, which includes diffuse functions of all types. So, for C in the aug-cc-pVTZ basis set, there are diffuse s, p, d, and f functions. The “jun-“ basis set omits the diffuse f functions along with all diffuse functions on H.

The great advantage of these trimmed basis sets is that they are smaller than the fully augmented sets, leading to faster computations. And since trimming off some diffuse functions leads to little loss in accuracy, one should seriously consider using these types of basis sets. As Truhlar notes, these trimmed basis sets might allow one to use a partially augmented but larger zeta basis set at the same cost of the smaller zeta basis that is fully augmented.


(1) Papajak, E.; Zheng, J.; Xu, X.; Leverentz, H. R.; Truhlar, D. G., "Perspectives on Basis Sets Beautiful: Seasonal Plantings of Diffuse Basis Functions," J. Chem. Theory Comput., 2011,
7, 3027-3034, DOI: 10.1021/ct200106a