Improvement of electronic structure calculations for the interpretation of the emission spectrum for NdIII complexes†
Yolimar
Gil, 
a
María José
Maldonado,
a
Ricardo Costa
de Santana,
b
Andrés
Vega,
c
Pablo
Fuentealba
*a
and
Daniel
Aravena
*d
a
María José
Maldonado,
a
Ricardo Costa
de Santana,
b
Andrés
Vega,
c
Pablo
Fuentealba
*a
and
Daniel
Aravena
*d
Abstract
A protocol to correct ab initio calculated luminescence spectra of NdIII complexes is proposed. The emission spectrum of [NdIII(bipy)(tta)3] was measured to calibrate the optimal correction for the Racah parameters on top of a CASSCF calculation to attain the best energetic placement of the 4F3/2 → 4I13/2−9/2 emission lines. As interelectronic repulsion is the most important source of error in this calculation, this straightforward correction results in an accurate placement of transitions, allowing the assignment of a complex spectral shape in terms of its underlying transitions. Finally, the correction derived for [NdIII(bipy)(tta)3] was directly applied to a different NdIII complex, demonstrating the broad use of this approach.
Please wait while we load your content...
