The electrically detected orbital spectrum of a mesoscopic silicon device containing a small number of donors has been investigated. The device was fabricated on silicon-on-insulator with an optically active channel containing [Formula: see text] substitutional bismuth centers introduced by ion implantation. The [Formula: see text] orbital transition at the energy associated with isolated bismuth donors was detected via a change in photocurrent when illuminated by THz light from a free electron laser. The spectral dependence on bias, temperature, and laser intensity is explored to determine optimum conditions for detecting orbital transitions in smaller devices with fewer donors. These results suggest that photo-induced impact ionization can offer a route for the spectroscopic detection of few impurities providing a useful tool for the development of solid-state quantum technologies.