Basis sets for geometry optimizations of second‐row transition metal inorganic and organometallic complexes

Abstract

AbstractModest‐sized basis sets for the second‐row transition metal atoms are developed for use in geometry optimization calculations. Our method is patterned after previous work on basis sets for first‐row transition metal atoms. The basis sets are constructed from the minimal basis sets of Huzinaga and are augmented with a set of diffuse p and d functions. The exponents of these diffuse functions are chosen to minimize both the difference between the calculated and experimental equilibrium geometries and the total molecular energies for several second‐row transition metal inorganic and organon etallic complexes. Slightly smaller basis sets, based on the same Huzinaga minimal sets but augmented with a set of diffuse s and p functions rather than diffuse p and d functions, are also presented. The performance of these basis sets is tested on a wide variety of second‐row transition metal inorganic and organometallic complexes and is compared to pseudopotential basis sets incorporating effective core potentials.