Study of Some Nd3+ Complexes: Interelectronic Repulsion, Spin–Orbit Interaction, Bonding, and Electronic Energy Levels

Abstract

The values of Slater–Condon (F2, F4, F6) and Racah (E1, E2, E3) interelectronic repulsion and Landé (ζ4f) spin–orbit interaction parameters have been computed from already observed visible and near infrared absorption spectra of 24 Nd3+ complexes. Using these parameters the energies of 27 energy levels of each complex have been calculated. The agreement between the computed and experimental energy levels is good (average deviation, 32–55 cm−1; rms deviation, 59–117 cm−1). The variation of all the parameters in the complexes from the corresponding Nd3+ “free” ion parameters has been discussed. The average values of F4 / F2 and F6 / F2 for Nd3+ complexes have been found to be ≃ 0.15 and ≃ 0.015, respectively, which are different from those calculated assuming wavefunctions to be hydrogenic or by using Hartee–Fock methods. Using F2 values the nephelauxetic ratio β and bonding parameter b1/2 have been calculated. The complexes have been arranged in increasing order of covalent bonding. For the same ligand the covalency decreases as the atomic number of the rare-earth metal ion increases.

Adsorption of Rare Earth Elements onto DNA-Functionalized Mesoporous Carbon

“…It was suggested earlier that the intensity of WL at the Nd L 2,3 -edges correlates with the partially covalent character of its chemical bonds with ligands. The 4f electrons in Nd 3+ complexes are not completely localized and interact weakly with ligand orbitals. , Therefore, the back-charge transfer from ligands to partly filled 4f­(Nd) orbitals occurs, leading to an increase in the screening effect of the excited photoelectron in the 5d-like state. As a result, the photoelectron wave function becomes more localized that promotes an increase in the transition matrix element between the 2p 3/2 (Nd) core level and the final state and, ultimately, increases the WL intensity .…”

Crystal field levels and magnetic anisotropy in the kagome compounds Nd3Sb3Mg2O14 , NdScheie1, Sanders2, Krizan3 et al. 2018Phys. Rev. B202240View full textAdd to dashboardCite

“…We finally attempted to account for the susceptibility discrepancy by including higher multiplet mixing in the CEF Hamiltonian. For Nd3+ the first excited multiplet (J = 11/2) is only at 230 meV [28], so it could conceivably effect the magnetism at high temperatures. To test this we re-fit and analyzed the data using an intermediate coupling scheme: including spin-orbit coupling and calculating eigenkets in the LS basis rather than the J basis.…”

Synthetic and Spectral Studies of Complexing Behavior of Isothio Cyanato Complexes of 4 [N-4-Ethoxy Benzalidine Amino] Antipyrine (C20h21n3o2)

“…The hypersensitive bands of the Nd (III) complex resemble that of nine and eight coordinate complexes reported by Karrakar 53 suggesting a coordination number of nine and eight around the metal ion in the complexes [54][55][56][57][58][59][60][61][62][63][64][65][66] .…”

“…The spectra show a shift of the band towards lower energy compared with those of the aqua ions owing to nephelauxetic effect 52 . The bonding parameter (b1/2) and the covalence parameter ( ) are less than unity while sinhas parameter () is positive indicating a moderate covalent character for the bond between 53 .…”