Infinite Basis Set Extrapolation for Double Hybrid Density Functional Theory 2: Effect of Adding Diffuse Basis Functions

Abstract

AbstractWe applied the Infinite Basis (IB) set extrapolation and Double Hybrid Density Functional Theory (DHDF) to calculate the electron affinities, reaction barrier heights, proton affinities, non‐covalent interactions, atomization, ionization, and alkyl bond dissociation energies. We previously found that the mean unsigned error of the B2KPLYP‐IB calculation with the combination of cc‐pVTZ and cc‐pVQZ reach the chemical accuracy limit (∼2 kcal/mol) where the largest deviation occurred in the electron affinity calculations and the weak interactions between noble gases and nonpolar molecules. Here, we investigated the basis set effect using the B2KPLYP‐IB extrapolation scheme that involves (1) the addition of extra tight d basis functions to the second row elements (i.e. cc‐pV(L+d)Z), (2) the addition of extra s, p, and d diffuse basis functions, and (3) a comparison between Dunning's Correlation Consistent and Jensen's Polarization Consistent (pc‐L) basis sets. We found that the addition of extra s and p diffuse basis functions formed the minimal augmented basis sets proposed by Truhlar. This addition permitted the B2KPLYP‐IB to reach the chemical accuracy limit with the combination of the double ζ and triple ζ basis sets. Adding extra s, p diffuse functions to the pc‐L series permitted only a small improvement. This small improvement is due to the fact that the pc‐L basis sets already contain a large number of functions for the p block elements. Taken together, the results suggest that this minimal augmented basis sets is useful for due to its accuracy and affordable computational cost.