Gaussian basis sets for molecular calculations. The representation of 3d orbitals in transitionmetal atoms
Abstract
Augmented (4d) and (5d) Gaussian basis sets are presented which provide a balanced description of the 4s^{2}3d^{n2}, 4s3d^{n1}, and 3d^{n} configurations of transitionmetal atoms. When compared to accurate HartreeFock calculations, the (4d) and (5d) expansions in the literature, which have been optimized for the 4s^{2}3d^{n2} configuration, can lead to errors of several eV for states of the latter configurations where the 3d orbitals become more diffuse. The augmented sets reported here consist of a single diffuse basis function added to the original sets, where the orbital exponent of the added function was optimized for the 3d^{n} configuration. Basis sets and contraction schemes are presented for the atoms Sc through Cu.
 Publication:

Journal of Chemical Physics
 Pub Date:
 May 1977
 DOI:
 10.1063/1.433731
 Bibcode:
 1977JChPh..66.4377H
 Keywords:

 Atomic Energy Levels;
 Electron Orbitals;
 Electron States;
 Transition Metals;
 Ground State;
 Hartree Approximation;
 Metal Compounds;
 Molecular Orbitals;
 Atomic and Molecular Physics;
 31.20.Ej