SummaryWe present a new model for the gas amplification effect used in many environmental scanning electron microscopes, wherein molecular complexity is shown to be the critical factor. Monte Carlo simulations, based on experimental electron scattering cross-sections, are used to deduce a predictive model for the amplification process that is superior to the Townsend gas capacitor model. These predictions are compared with experimentally obtained amplification curves. Significantly, it is shown that the ionization efficiency of the electrons changes dramatically over the gap distance, and a constant value cannot be assumed. Atomic and molecular excitations affect the amplification process in two ways: first, they serve to lower the average kinetic energy of the imaging electrons, thereby keeping a greater fraction near the ionization threshold energy. Second, molecular normal modes determine the effectiveness of positive gas ions in producing additional secondaries upon surface impact. Practical implications such as signal gain and fraction of useful signal as a function of operating conditions are discussed in the light of the new model. Finally, we speculate on potential new contrast mechanisms brought about by the presence of an imaging gas.