Complete Excitation of Discrete Quantum Systems by Single Free Electrons.

We reveal a wealth of nonlinear and recoil effects in the interaction between individual low-energy electrons (≲100  eV) and samples comprising a discrete number of states. Adopting a quantum theoretical description of combined free-electron and two-level systems, we find a maximum achievable excitation probability of 100%, which requires specific conditions relating to the coupling strength and the transition symmetry, as we illustrate through calculations for dipolar and quadrupolar modes. Strong recoil effects are observed when the kinetic energy of the probe lies close to the transition threshold, although the associated probability remains independent of the electron wave function even when fully accounting for nonlinear interactions with arbitrarily complex multilevel samples. Our work reveals the potential of free electrons to control localized excitations and delineates the boundaries of such control.