The general‐purpose Monte Carlo code PENELOPE for the simulation of coupled electron and photon transport is used to generate x‐ray emission spectra from targets irradiated by electrons. This code provides a realistic description of the penetration and slowing down of electrons with energies in the range from ∼ 1 keV to 1 GeV. The simulation of bremsstrahlung emission is based on numerical partial‐wave cross sections, differential in both the photon energy and the direction of emission. The ionization of K and L shells by electron impact is simulated by using total ionization cross sections calculated from the distorted‐wave first Born approximation; these cross sections, which are different from those in the public version 2001 of PENELOPE, provide a better description of the ionization process. The relaxation of ionized atoms is accounted for by combining transition probabilities from the LLNL Evaluated Atomic Data Library with experimental x‐ray energies. A systematic comparison of simulated x‐ray spectra with absolute spectra measured with an electron microprobe, for various elemental solid targets and 20 keV electron beams will be presented. The discrepancies between Monte Carlo results and experiment will be discussed.

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