PES OF HIGH-TEMPERATURE VAPORS .8. TRANSITION-METAL DIHALIDES

The He 1 protoelectron spectra of transition metal halide vapors MX 2 (M = Mn, Fe, Co, Ni; X = Cl, Br) are presented. The spectra are interpreted by comparing the experimental ionization energies with transition state eigenvalues calculated by the multiple scattering scheme, using a cellular (but not muffin tin) partitioning of space. Satisfactory correlation between theory and experiment is achieved when the calculations are carried out with spin-polarized orbitals. This correlation leads to the conclusion that the metal 3d orbitals contribute predominantly to the uppermost occupied orbitals for MnX2, FeX2, and CoX2, but they are drawn deeper in NiX2 and become corelike orbitals at ZnX2, the full d shell. © 1979 American Institute of Physics.