Theoretical investigation of optical and paramagnetic resonance spectra of [NiF6](4-) clusters with orthorhombic symmetry.

The ground state absorption spectra of [NiF6](4-) clusters with orthorhombic symmetry (Ni(2+) in NiF2 crystal and Ni(2+)-doped ZnF2 crystal, D2h point group) are theoretically calculated and assigned by diagonalization of 45×45 complete energy matrix for 3d(8) configuration and the spin-Hamiltonian (SH) parameters (zero-field splitting D and E, and g factors gx, gy, gz) are studied by use of high-order perturbation method, in the frame of semi-empirical molecular orbital (MO) scheme based on strong crystal field framework. In those energy matrix, all the configuration interactions though the cubic crystal field (CF), the orthorhombic crystal field, the Coulomb interaction are taken into account. The calculated results are in good agreement with the experimental data. The local structure (bond length and bond angle) of [NiF6](4-) clusters are determined, and the results shows that the structure data given by Stout are more plausible than those given by Baur.

Theoretical investigations of optical spectra and electron paramagnetic resonance spectra of LiCl:Ni²âº crystals.

The complete energy matrices (45 × 45) including low symmetry ligand field (C(4v)) and Coulomb interactions for 3d(8) ions have been constructed, and the high-order perturbation formulas of spin-Hamiltonian (SH) parameters g factors g(//), g(⊥) and zero-field splitting (ZFS) parameter D for ground state (3)A(2g) of the 3d(8) ions in the tetragonal symmetry environment have been derived. In those formulas both the crystal field (CF) mechanism and the charge transfer (CT) mechanism are taken into account. The complete energy matrices and the high-order perturbation formulas are applied to calculate the energy levels and SH parameters of the Ni(2+) ion in LiCl crystal respectively. The results are in reasonable agreement with the experimental data and indicate that CT mechanism plays important role in the understanding of SH parameters, especially the g factors. All the multiplet energy are assigned theoretically and the local structures of LiCl:Ni(2+) are established.