Crystals field energy levels and transition line strengths of neodymium in trigonal Na 3[Nd(oxydiacetate) 3]·2NaClO 4·6H 2O

Abstract

Locations and assignments of 119 crystal-field levels are reported for Nd 3+ in the trigonal Na 3[Nd(oxydiacetate) 3]·2NaClO 4·6H 2O levels span 34 of the 37 J-multiplet manifolds split out of the 4f 3 electronic configuration of Nd 3+ between 0 and 40000 cm −1, and they were located and assigned from axial and orthoaxial (σ- and π-polarized) absorption measurements performed on single crystals at temperatures between 4.2 and 300 K. The energy level data are analyzed in terms of a parameterized model Hamiltonian for the 4f 3 electronic configuration, assumed to be perturbed by a crystal field of trigonal dihedral (D 3) symmetry. Parametric fits of calculated to empirical energy level data yields rms deviations (between calculated and observed energies) of ≈ 14 cm −1 for 119 levels and ≈ 12 cm −1 for the subset of 71 levels that derive from multiplet manifolds with J ⩽ 9/2. The Hamiltonian parameter values obtained from these energy level analyses are reported and are compared with results obtained from similar analyses of Nd 3+ in other crystals and of other Ln 3+ ions in the Na 3[Ln(oxydiacetate) 3]. 2NaClO 4·6H 2O system. In addition to energy level locations and assignments, quantitatively determined line strengths are reportedfor 47 trans low-temperature π-polarized orthoaxial absorption spectra. All of these transitions originate in the ground crystal-field level of the 4I 9 2 (ground) multiplet, and each occurs via a predominantly electric-dipole mechanism.