Model potentials for molecular calculations. I. The <i>sd</i>‐MP set for transition metal atoms Sc through Hg

Abstract

Abstract Model potential parameters and valence orbitals were generated for the transition metal atoms Sc through Hg. Only the nd and ( n + 1) s valence electrons were treated explicitly and the effects of the remaining electrons were replaced by model potentials. For brevity they may be called sd ‐MPs. Major relativistic effects were incorporated on the level of Cowan and Griffin's quasirelativistic Hartree‐Fock (QRHF) method for the second and third transition metal atoms. The model potential parameters and valence orbitals were determined so as to reproduce the results of the numerical Hartree‐Fock reference calculations. The obtained valence orbitals have inner nodal structure. The model potential method can yield a balanced description of the s 2 d n –1 , sd n , and d n + 1 configurations of the atoms. The polarization functions were also generated for the use in molecular calculations.