Identification of doped paramagnetic vanadyl impurity in dipotassium diaquabis(malonato-κ²O,O′) zincate dihydrate single crystal using EPR and optical techniques

Abstract

Identification of doped paramagnetic vanadyl impurity in dipotassium diaquabis(malonato-κ 2 O,O′) zincate dihydrate single crystal using EPR and optical techniques, Single crystal electron paramagnetic resonance (EPR) spectroscopic investigation of VO(II) doped dipotassium diaquabis(malonato-κ 2 O,O ) zincate dihydrate has been carried out at X-band frequencies at 300 K. Single crystal, rotated along the three orthogonal crystallographic axes, has yielded spin Hamiltonian parameters g and A as g xx = 1.978, g yy = 1.972, g zz = 1.936 and A xx = 7.12, A yy = 6.73, A zz = 18.24 mT, respectively. These spin Hamiltonian parameters reflect a slight deviation from axial symmetry to rhombic, which is explained by the interstitial occupation of vanadyl ions. The isofrequency plots and powder EPR spectrum have been simulated using the calculated spin Hamiltonian parameters. The percentage of metal-oxygen bond has been estimated to be 20%. The admixture coefficients and bonding parameters have also been calculated by combining the EPR data with optical data.

Molecular structure identification and position of a dopant ion in diaqua(2,2′-bipyridine)malonatozinc(II) by spectroscopic studies – II: VO(II)

“…A good agreement was obtained indicating the accuracy of the spin Hamiltonian parameters. These spin Hamiltonian parameters were in agreement with other literature values [21][22][23].…”

Single-crystal electron paramagnetic resonance study of the interstitial position of Mn(II) in dipotassium diaquabis(malonato-κ2O,O′) zincate(II) dihydrate

“…This study was then extended to find the energies of various orbital levels, which, in comparison with the EPR data, explains the nature of bonding in the complex. The present study has significance since the vanadyl ion has entered the PMZD lattice interstitially [18].…”

The substitutional occupation of vanadyl ion in diaquamalonatozinc(II)—single crystal EPR and powder optical studies

“…The calculated values of β 2 1 and ε 2 indicate that the in-plane σ -bonding is moderately ionic and out-of plane π-bonding is significantly covalent. The calculated values of β 2 1 , ε 2 , P and k are listed with similar lattices [37,[39][40][41] for comparison in table 5. The parameter k indicates extreme sensitivity to the deformations of the electron orbitals of the central vanadium ion.…”