Calculation of the electron spin resonance parameters of the first row transition metal pentacyanonitrosyls through and INDO SCF MO calculation

Abstract

The spin Hamiltonian parameters g∥,g⊥, A(M), B(M), A(¹⁴N) and B(¹⁴N) of some isoelectronic d⁵ first row transition metal pentacyanonitrosyls are theoretically evaluated from an unrestricted Hartree–Fock SCF MO calculation of the INDO type. The agreement between the experimental data reported and the calculated values, especially for metal hyperfine coupling constant in both magnitude and sign, is quite good. Even the small ligand hyperfine splittings due to the ¹⁴N of the axial N—O group could be calculated with reasonable accuracy from the unpaired spin distributions obtained in the basic valence orbitals of the nitrogen ligand in agreement with the experiment.