Combined bond polarization function basis sets for accurate ab initio calculation of the dissociation energies of AHn molecules (A=LI to F)

Abstract

AbstractAn alternative route toward developing basis sets for post‐Hartree‐Fock calculations, the hybrid bond polarization function method, is investigated. Two new basis sets, denoted 6‐31G(d, p)+ B and 6‐31 + G(d,p)+B, are defined for the first‐row hydrides. The dissociation energies of the first‐row hydride species in their respective ground states are computed using full fourth‐order Møller‐Plesset theory, and compared with results obtained with large polarized basis sets containing no bond functions. It is shown that results are competitive even with basis sets as large as 6‐311++G(3df,3pd), while computation times are reduced by a factor of 4 to 20. On empirical grounds, the basis set superposition error should be neglected entirely.