This paper presents results from the calculation of the high-energy electron–electron scattering rate in silicon based on a full energy-band structure obtained by the pseudopotential technique. The effects on the scattering rate of the overlap integrals, wave-vector-dependent dielectric function and umklapp processes are described and the transition rate is compared with that obtained using a semiclassical analysis based on a parabolic energy dispersion. A hybrid Monte Carlo/iterative technique for solving the Boltzmann transport equation is used to obtain the electron energy distribution function generated by binary particle interactions in a one-dimensional system. ©1997 American Institute of Physics.