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

Abstract

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.