Basis set effects on calculated geometries: 6-311++G** vs. aug-cc-pVDZ

The effect of basis sets on MP2 and CCSD calculated geometries has been investigated for a series of small organic molecules with two to four nonhydrogen atoms. Whereas 6-311 + +G** usually leads to satisfactory structures, this was not true with aug-cc-pVDZ, although it uses more basis functions than the former set. In addition, the smaller 6-311 + +G** invariably leads to lower calculated energies than aug-cc-pVDZ. With a given basis set, CCSD gives more satisfactory calculated geometries than MP2, but with a much greater computation time. For the compounds in this report, B3LYP/6-311++G** is quite effective in giving satisfactory calculated geometries at a relatively small computational cost. (C) 2004 Wiley Periodicals, Inc.