On the Experimental Determination of 4f-4f Intensity Parameters from the Emission Spectra of Europium (III) Compounds


Eu3+ complexes and specially beta-diketonate compounds are well known and studied in several areas due to their luminescence properties, such as sensors and lightning devices. A unique feature of the Eu3+ ion is the experimental determination of the 4f-4f intensity parameters Omega(lambda) directly from the emission spectrum. The equations for determining Omega(lambda) from the emission spectra are different for the detection of emitted power compared to modern equipment that detects photons per second. It is shown that the differences between Omega(lambda) determined by misusing the equations are sizable for Omega(4) (ca. 15.5%) for several Eu3+ beta-diketonate complexes and leads to differences of ca. 5% in the intrinsic quantum yields Q(Ln)(Ln). Due to the unique features of trivalent lanthanide ions, such as the shielding of 4f-electrons, which lead to small covalency and crystal field effects, a linear correlation was observed between Omega(lambda) obtained using the emitted power and photon counting equations. We stress that care should be exercised with the type of detection should be taken and provide the correction factors for the intensity parameters. In addition, we suggest that the integrated intensity (proportional to the areas of the emission band) and the centroid (or barycenter) of the transition for obtaining Omega(lambda) should be determined in the properly Jacobian-transformed spectrum in wavenumbers (or energy). Due to the small widths of the emission bands of typical 4f-4f transitions, the areas and centroids of the bands do not depend on the transformation within the experimental uncertainties. These assessments are relevant because they validate previously determined Omega(lambda) without the proper spectral transformation.




Optics; Spectroscopy


Blois, L; Neto, ANC; Longo, RL; Costa, IF; Paolini, TB; Brito, HF; Malta, OL

nossos autores


The authors thank the Brazilian funding agencies: Conselho Nacional do Desenvolvimento Cientifico e Tecnologico (CNPq), Coordenacao de Aperfeicoamento de Pessoal de Nivel Superior (CAPES), and Fundacao de Amparo a Pesquisa do Estado de Sao Paulo (FAPESP). L. Blois is grateful to FAPESP for the Ph.D. scholarship (Grant 2020/16795-6). A.N. Carneiro Neto is thankful to SusPhotoSolutions-Solucoes Fotovoltaicas Sustentaveis, CENTRO-01-0145-FEDER-000005. R.L. Longo is grateful for the partial financial support under grants: Pronex APQ-0675-1.06/14, INCT-NANOMARCS APQ-05491.06/17, APQ-1007-1.06/15, and CNPq-PQ fellowship (Grant 309177/2018-9). I.F. Costa is grateful to CNPq for his post doctorate scholarship (Grant 151623/2020-1). H.F. Brito is grateful to CNPq for the research grant (306951/2018-5). L. Blois also thanks Prof. Erick Bastos and Frank Quina (Instituto de Quimica-USP) for making the Edinburgh FLS980 Fluorometer available. The authors are thankful to the Analytical Central of the Institute of Chemistry (Central Analitica-IQUSP) for the elemental and mass spectrometry analyses. This paper is dedicated to Professor Marina Popova.

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