The sensitivity of B3LYP atomization energies to the basis set and a comparison of basis set requirements for CCSD(T) and B3LYP

Abstract

The atomization energies of the 55 G2 molecules are computed using the B3LYP approach with a variety of basis sets. The 6–311 + G(3df) basis set is found to yield superior results to those obtained using the augumented-correlation-consistent valence-polarized triple-zeta set. The atomization energy of SO 2 is found to be the most sensitive to basis set and is studied in detail. Including tight d functions is found to be important for obtaining good atomization energies. The results for SO 2 are compared with those obtained using the coupled-cluster singles and doubles approach including a perturbational estimate of the triple excitations.