6-31G*basis set for third-row atoms

Medium basis sets based upon contractions of Gaussian primitives are develo ped for the third-row elements Ga through Kr. The basis functions generaliz e the 6-31G and 6-31G* sets commonly used for atoms up to Ar. A reexaminati on of the 6-31G* basis set for K and Ca developed earlier leads to the incl usion of 3d orbitals into the valence space for these atoms. Now the 6-31G basis for the whole third-row K through Kr has six primitive Gaussians for 1s, 2s, 2p, 3s, and 3p orbitals, and a split-valence pair of three and one primitives for valence orbitals, which are 4s, 4p, and 3d. The nature of th e polarization functions for third-row atoms is reexamined as well. The pol arization functions for K, Ca, and Ga through Kr are single set of Cartesia n d-type primitives. The polarization functions for transition metals are d efined to be a single 7f set of uncontracted primitives. Comparison with ex perimental data shows good agreement with bond lengths and angles for repre sentative vapor-phase metal complexes. (C) 2001 John Wiley & Sons, Inc.