Role of vitreous matrix on the optical activity of Ge-doped silica Original Research Article

We report an experimental study on the relationship between the optical activity of Ge-oxygen deficient centers and dynamic properties and conformational heterogeneity of vitreous matrix in silica. We focus our attention on the absorption band at ∼5.2 eV (B2β) and on the two related emissions at ∼4.2 eV (αE) and at ∼3.1 eV (β). From the temperature dependence of B2β band we estimate a mean energy value of 26 meV for local vibrational modes coupled to the electronic transition, suggesting that the chromophore and its surrounding have access to low frequency dynamics. From the thermal behavior of the two emissions we distinguish the two competitive relaxation processes from the first singlet excited state S1: the radiative one, giving rise the αE band, and the thermally activated intersystem-crossing process between S1 and the triplet state T1, originating the β band. The intersystem-crossing rate increases on increasing the temperature, determining an opposite thermal behavior of the intensity of the two emissions. However, this temperature dependence cannot be rationalized by a simple Arrhenius law and the αE decay kinetics at high temperatures do not follow a single exponential law, suggesting a complex landscape of configurational energies of the process.