A general kinetic theory is used to explain the shapes of photoionized sample luminescence curves perturbed by thermal jumps (Δ ∼ 1 K, rise time ∼ 1 s). The samples studied are photoactivated organic vitreous solutions of TMPD/MCH 10−3 M and TMPD/3-MP 10−3 M. The experiments are performed within a temperature range (63–91 K) which includes the glass transition temperature Tg. It is shown that there is a slow diffusion of the trapped electrons towards the cation and competition between thermal detrapping and tunneling. The tunneling/thermal detrapping ratio Y is not time dependent during an isothermal luminescence and is only slowly temperature dependent if T ≤ Ty. Ty is very close to Tg. For T > Ty, Y decreases rapidly with T. The activation energy for thermal detrapping shows a maximum when the temperature reaches [Formula: see text] The glass transition temperature Tg may therefore be defined empirically as:[Formula: see text]Finally we obtain a glassy matrix relaxation time, τ, which decreases with T.
