We investigate the excited state electronic structure of the model phase transition system In/Si(111) using femtosecond time-and angle-resolved photoemission spectroscopy (trARPES). An extreme ultraviolet 500 kHz laser source at 21.7 eV is utilized both to map the energy of excited states above the Fermi level and follow the momentum-resolved population dynamics on a femtosecond timescale. Excited-state band mapping is used to characterize the normally unoccupied electronic structure above the Fermi level in both structural phases of In/Si(111): the metallic (4 x 1) and the gapped (8 x 2) phases. The extracted band positions are compared with band-structure calculations utilizing density functional theory within both the local density approximation and GW approximations (single-particle Green's function (G) + screened Coulomb interaction (W)). While good overall agreement is found between the GW-calculated band structure and experiment, deviations in specific momentum regions may indicate the importance of excitonic effects not accounted for at this level of approximation. To probe the dynamics of these excited states, their momentum-resolved transient population dynamics are extracted with trARPES. The transient intensities are compared to a simulated spectral function modeled by a state population employing a transient elevated electronic temperature as determined experimentally. This allows the momentum-resolved population dynamics to be quantitatively reproduced, revealing important insights into the transfer of energy from the electronic system to the lattice. In particular, a comparison between the magnitude and relaxation time of the transient electronic temperature observed by trARPES with those of the lattice as probed in previous ultrafast electron diffraction studies implies a highly nonthermal phonon distribution at the surface following photo-excitation. This suggests that the energy from the initially excited electronic system is initially transferred to high-energy optical phonon modes followed by cooling and thermalization of the photo-excited system by much slower phonon-phonon coupling.