An improved 6-31G(*) basis set for first-row transition metals

by Mitin, A. V.; Baker, J.; Pulay, P.

We propose a modification to the popular 6-31G(*) basis set, which has recently been extended to cover first-row transition metals [Rassolov , J. Chem. Phys. 109, 1223 (1998)]. As demonstrated by a number of calculations, the existing basis performs poorly for many transition metals, particularly those toward the end of the series (Co, Ni, and especially Cu). The reason for this lies primarily with the 3D shell, which lacks a sufficiently diffuse exponent. A reoptimization of the D-shell exponents and coefficients by a two-step procedure, keeping the rest of the basis unchanged, corrects the problem, giving a basis set that performs uniformly well across the entire first-row transition metal series from scandium to copper.

Journal
Journal of Chemical Physics
Volume
118
Issue
17
Year
2003
Start Page
7775-7782
URL
https://dx.doi.org/10.1063/1.1563619
ISBN/ISSN
1089-7690; 0021-9606
DOI
10.1063/1.1563619