An ESR study of [V(CN)5NO]4− in γ‐irradiated K3V(CN)5NO⋅2H2O

An ESR study of electron damaged K3V(CN)5NO⋅2H2O shows the presence of a d5 species V(CN)5NO4− with the spin Hamiltonian parameters g∥ = 1.974, g⊥ = 2.0007, A (51V) = −116.03×10−4 cm−1, B (51V) = −43.76×10−4 cm−1, A (14N) = −1.8×10−4 cm−1, and B (14N) = −6.42×10−4 cm−1. Results of a simplified semiempirical molecular orbital approach have been used to correlate the experimental spin Hamiltonian parameters of the isoelectronic d5 series from vanadium to iron. In addition, the ligand hyperfine splittings due to 14N have been explained on the basis of a configuration interaction mechanism.