Secondary electron emission from copper is probed utilizing Monte Carlo simulations that take account of elastic scattering based on the Mott theory and inelastic collisions based on energy-dependent energy loss functions. The loss function and stopping power were obtained through first-principles density functional theory. Angular assignment of electrons following elastic scattering or the creation of secondaries is shown to affect the energy-dependent secondary electron yield (SEY). A good match of the simulation results (with a peak SEY of ~180% at around 300 eV and less than 10% deviation over the 0 to 1000 eV energy range) to available experimental data is shown based on an energy and momentum conservation scheme. Also, the distribution of delay times for the generation of secondaries, the SEY behavior at different incident angles, the energy distribution of emergent secondaries, and their creation profiles as a function of depth are computed to provide a more complete picture of the governing mechanisms and predicted responses.