Systematic Determination of the Slater Parameters for the First Transition Elements

Abstract

Slater's parameter $F^k$ and $G^k$ with $\mathrm{k\hspace{0.17em}\ne O}$ have been determined systematically from the experimental atomic energy levels for the neutral atoms and singly through triply positive ions of the first transition elements in their ${\text{3d}}^n$ , ${\text{3d}}^{\text{n−1}}\text{4s}$ , ${\text{3d}}^{\text{n−1}}\text{4p}$ , ${\text{3d}}^{\text{n−2}}\text{4s4p}$ , and ${\text{3d}}^{\text{n−2}}{\text{4s}}^2$ . configurations, by a least‐squares procedure. A procedure of obtaining the semiempirical values of $F^0\text{'}\mathrm{s}$ , which have never been obtained from the data of atomic spectra, is given along the line suggested by Anno [J. Chem. Phys. 47, 5335 (1967)] involving the consideration of appropriate “electron‐transfer reactions.” Data on $\mathrm{\Delta E}$ , the energy change in the course of the electron‐transfer reaction, are also given, which may be combined with $F^k\text{'}\mathrm{s}$ and/or $G^k\text{'}\mathrm{s}\text{(k\hspace{0.17em}≠\hspace{0.17em}0)}$ to obtain $F^0\text{'}\mathrm{s}.$ Ideal correlation lines, which correlate a particular kind of $F^k$ , $G^k\text{(k\hspace{0.17em}≠\hspace{0.17em}0)}$ , or $\mathrm{\Delta E}$ with the atomic number $Z$ and/or electron configuration in ideal situations where no anomaly due such as to CI or misassignment were present, are discussed and are given in such a way that they are most consistent with the actual data obtained to facilitate the semiempirical MO calculations on the transition metal compounds, in which the metal atom has a fractional charge and a fractional population in each of its AO's. As far as possible, the semiempirical data obtained in the present work have been compared with the data obtained with the nonempirical Hartree–Fock calculations.