Intensity of cooperative vibronic transitions in the Eu(III), Gd(III) and Tb(III) formates spectra

The luminescence and absorption spectra of the lanthanide ions in solids and coordination compounds are characterized by sharp pure electronic lines, which are accompanied by much weaker lines of vibronic transitions. The vibronic spectroscopy is a good probing tool for investigations of the properties of surrounding ion ligands. The lanthanides formates are efficient luminescent crystals and can be viewed as the elementary type in the whole class of the oxygen-containing lanthanide coordination compounds. The intensity of vibronic transitions in spectra of luminescence and excitation europium (5 D0 →7 F2 , 7 F0 →5 D2 ), terbium (7 F6 →5 D4 ), gadolinium (6 P7/2 →8 S7/2 ) in anhydrous formates of the type Ln(HCOO)3 (Ln = Eu, Tb, Gd) and Y(HCOO)3 .2H2 O doped with Eu3+ and Tb3+ (C ~1 mol%) are reported. Also, the infrared and Raman spectra were obtained for the same compounds. Related integral intensity vibronic sidebands depend on the type of electronic transition of the same ion and varies for the same electronic transitions in different crystals. The obtained experimental data referring to the rate constants of vibronic transitions and intensity distribution in vibronic spectra on normal vibrations of the formate groups are in agreement with the predictions based on the Stavola-Dexter theory of cooperative vibronic transitions.