In this work, the direct simulation Monte Carlo (DSMC) method is used to model the physical vapor deposition of titanium using electron-beam evaporation. Titanium atoms are vaporized from a molten pool at a very high temperature and are accelerated collisionally to the deposition surface. The electronic excitation of the vapor is significant at the temperatures of interest. Energy transfer between the electronic and translational modes of energy affects the flow significantly. The electronic energy is modeled in the DSMC method and comparisons are made between simulations in which electronic energy is excluded from and included among the energy modes of particles. The experimentally measured deposition profile is also compared to the results of the simulations. It is concluded that electronic energy is an important factor to consider in the modeling of flows of this nature. The simulation results show good agreement with experimental data.