Combined bond‐polarization basis sets for accurate determination of dissociation energies. II. Basis set superposition error as a function of the parent basis set

Abstract

AbstractThe effect of the parent basis set on the basis set superposition error caused by bond functions is investigated systematically. An important difference between BSSE at the SCF and correlated levels is pointed out. Three new basis sets are defined, denoted 6‐311 + G(d,p)B, 6‐311 + G(2d,p)B, and 6‐311 + G(2df,p)B. BSSE for the first‐row hydrides seems to increase uniformly with increasing atomic number of the central atom. Expansion of the valence part of the basis set from 6‐31G to 6‐311G, as well as adding f functions, has a significant effect on the BSSE. Additional BSSEs incurred by bond functions are less than or equal to 1 kcal/mol for the 6‐311 + G(2df,p)B basis set. For the dissociation energies of the first‐row hydride species, agreement with experiment within only a few kcal/mol can be obtained even without resorting to isogyric reaction cycles. For high‐quality calculations, adding bond functions seems to have definite advantages over expanding the polarization space beyond the [2d1f] level.